Polymer polyol composition, process for producing the same, and process for producing polyurethane resin

ABSTRACT

This invention provides a polymer polyol composition (I) comprising a polyol (A) and polymer particles (B) dispersed in (A), the polymer particles (B) being formed by polymerizing an ethylenically unsaturated compound (b) in a polyol, wherein the content of (B) in (I) is from 35 to 75 mass %, based on the mass of (I), and the amount of soluble polymers (P) dissolved in (A) is not more than 5 mass %, based on the mass of (A), and provides methods for producing the polymer polyol composition (I). Further, this invention provides a method for producing a foamed or non-foamed polyurethane resin, which method comprises reacting a polyol component with a polyisocyanate component in the presence or absence of a blowing agent, wherein the above polymer polyol composition is used at least as a portion of the polyol component. A polymer polyol having a low viscosity and excellent dispersion stability is provided even when having a high concentration of polymer particles, and is used advantageously to produce polyurethane resins having excellent 25% ILD (hardness) and compression set, or foams thereof, with good operation efficiency.

TECHNICAL FIELD

[0001] The present invention relates to polymer polyol compositions forproducing polyurethane resins, methods for producing the polymer polyolcompositions, and a method for producing polyurethane resins or foamsthereof using the obtained polymer polyols.

BACKGROUND ART

[0002] Polymer compositions or mixtures obtained by polymerizing anethylenically unsaturated compound in a polyol are generally referred toas polymer polyols, and are used widely as the materials of polyurethaneresins such as polyurethane foams or polyurethane elastomers.

[0003] It is known that the content of polymer particles in a polymerpolyol may be increased to produce a polymer polyol that provides a highquality polyurethane with a greater hardness and a higher elasticmodulus. Known methods to obtain such a polymer polyol include a methodof polymerizing a vinyl monomer in the presence of a modified polyol, aportion of which has been allowed to react with a coupling agent (asilicon-containing compound, tetrakisalkoxy orthoformate,trialkoxyalkane, dialkoxyalkane, or the like) to increase its molecularweight (e.g. WO 85/04891), a method of polymerizing a vinyl monomer inthe presence of a macromer containing an urethane bond (e.g. JP61(1986)-115919 A), etc.

[0004] However, the polymer polyol compositions obtained by the abovemethods have deficiencies such as poor dispersion stability ordeteriorated miscibility with an isocyanate when forming a polyurethaneresin, and there were difficulties in handling. Thus, it has beendifficult to obtain a polymer polyol composition having good dispersionstability even when the content of polymer particles is high.

[0005] The inventors of the present invention have made earnestinvestigations to solve the above problems, and found that a polymerpolyol composition that provides a high quality polyurethane and has alow viscosity can be obtained by having a content of oligomers of notmore than a specified amount, thus reaching the present invention.Furthermore, it was also found that the same polymer polyol compositioncan be obtained by mechanically dispersing or crushing a polymer polyolobtained by polymerizing a monomer in the presence of a specificdispersant, thus reaching the present invention.

[0006] Furthermore, the inventors found that the use of a specificcompound having an ethylenically-unsaturated group at a terminal(hereinafter referred to as terminal ethylenically-unsaturated groupcontaining compound) and/or a specific reactive dispersant allows thesame polymer polyol composition to be obtained, thus providing thepresent invention.

[0007] It is an object of the present invention to provide polymerpolyols having a low viscosity and very good dispersion stability evenwhen the concentration of the polymer particles is high, and to providemethods for producing the polymer polyols. Also, it is another object ofthe present invention to provide a method for producing polyurethaneresins using these polymer polyol compositions or foams thereof, whereinthe polyurethane resins or foams thereof have good operation efficiencyand have high 25% ILD (hardness) and small compression set.

SUMMARY OF THE INVENTION

[0008] The present invention is as follows.

[0009] [First Invention] A polymer polyol composition (I) comprising adispersion medium composed of a polyol (A), or (A) and a diluent (C),and polymer particles (B) dispersed in the dispersion medium, whereinthe polymer particles (B) are formed by polymerizing an ethylenicallyunsaturated compound (b) in a polyol, or in a polyol and the diluent(C); the content of (B) in (I) is from 35 to 75 mass %, based on themass of (I); and the amount of soluble polymers (P) dissolved in (A) isnot more than 5 mass %, based on the mass of (A).

[0010] [Second Invention] A polymer polyol composition (I) comprising adispersion medium composed of a polyol (A), or (A) and a diluent (C),and polymer particles (B) dispersed in the dispersion medium, whereinthe polymer particles (B) are formed by polymerizing an ethylenicallyunsaturated compound (b) in a polyol, or in a polyol and (C); thecontent of (B) in (I) is from 35 to 75 mass %, based on the mass of (I);and the viscosity V (mPa·s) of (I) measured by a Brookfield viscosimeterat 25° C. is in the range of an inequality

V≦(Va−Va×C/10){circumflex over ( )}[e{circumflex over ( )}x],  (1)

[0011] where x=0.0010354×Bp{circumflex over ( )}1.5,

[0012] Va is a viscosity (mPa·s) of (A) measured by a Brookfieldviscosimeter at 25° C.,

[0013] C is a content of (C) in (I) (mass %),

[0014] Bp is a content of (B) in (I) (mass %),

[0015] symbol {circumflex over ( )} indicates a power, and

[0016] symbol “e” is the base of the natural logarithm.

[0017] [Third Invention] A polymer polyol composition (II) comprising apolyol (A), and polymer particles (B) dispersed in a dispersion mediumcomposed of a polyol (A), or (A) and a diluent (C), wherein the polymerparticles (B) are formed by polymerizing an ethylenically unsaturatedcompound (b) in a polyol; (b) contains at least 5 mass % of anethylenically unsaturated compound (b1) having a number-averagemolecular weight of at least 500; and (b) is polymerized in the presenceof a dispersant (D), and in the presence or absence of a diluent (C).

[0018] [Fourth Invention] A polymer polyol composition (III) comprisinga polyol (A), and polymer particles (B) dispersed in a dispersion mediumcomposed of a polyol (A), or (A) and a diluent (C), wherein the polymerparticles (B) are formed by polymerizing an ethylenically unsaturatedcompound (b) in a dispersion medium comprising (A) in the presence of adispersant (D′) to form polymer particles, and mechanically dispersingor crushing the polymer particles, and wherein the difference betweenthe solubility parameter SPd of (D′) and the solubility parameter SPa of(A) is not more than 0.8.

[0019] [Fifth Invention] A method for producing a polymer polyolcomposition, which method comprises polymerizing an ethylenicallyunsaturated compound (b) in a polyol (A) in the presence or absence ofat least one selected from a dispersant (D) and a diluent (C), whereinthe polymer polyol composition (I) or (II) of any of the first, secondand third inventions is obtained using (b) containing at least 5 mass %of an ethylenically unsaturated compound (b1) having a number-averagemolecular weight of at least 500.

[0020] [Sixth Invention] A method for producing the polymer polyolcomposition (I) of the first or second invention comprising a polyol (A)and polymer particles (B) dispersed in (A), which method comprisesseparating the polymer particles (B) from a polymer polyol compositionobtained by polymerizing an ethylenically unsaturated compound (b) in apolyol; and mechanically dispersing the polymer particles (B) in (A) notcontaining more than 5 mass % of soluble polymers, based on the mass of(A).

[0021] [Seventh Invention] A method for producing the polymer polyolcomposition (III) of the fourth invention, which method comprisespolymerizing an ethylenically unsaturated compound (b) in a dispersionmedium comprising a polyol (A) in the presence of a dispersant (D′) toform polymer particles in a polymer polyol; and mechanically dispersingor crushing the polymer particles, wherein the difference between thesolubility parameter SPd of (D′) and the solubility parameter SPa of (A)is not more than 0.8.

[0022] [Eighth Invention] A polymer polyol composition comprising adispersion medium composed of a polyol (A), or (A) and a diluent (C),and polymer particles (B) dispersed in the dispersion medium, whereinthe polymer particles (B) are formed by polymerizing an ethylenicallyunsaturated compound (b) in the dispersion medium in the presence orabsence of a dispersant (D), wherein at least 5 mass % of (b) comprisesa terminal ethylenically-unsaturated group containing compound (b3)having a number-average molecular weight of 160 to 490 and a solubilityparameter SPb of 9.5 to 13.

[0023] [Ninth Invention] A polymer polyol composition comprising adispersion medium composed of a polyol (A), or (A) and a diluent (C),and polymer particles (B) dispersed in the dispersion medium, whereinthe polymer particles (B) are formed by polymerizing the ethylenicallyunsaturated compound (b) in the dispersion medium, in the presence of0.5 to 50 mass parts of a reactive dispersant (D1) with respect to 100mass parts of (A), the reactive dispersant (D1) being an unsaturatedpolyol having a nitrogen-containing bond, which is formed by bonding asubstantially saturated polyol (a) with a monofunctional active hydrogencompound (e) having at least one polymerizable unsaturated group via apolyisocyanate (fi).

[0024] [Tenth Invention] A polymer polyol composition comprising adispersion medium composed of a polyol (A), or (A) and a diluent (C),and polymer particles (B) dispersed in the dispersion medium, whereinthe polymer particles (B) are formed by polymerizing the ethylenicallyunsaturated compound (b) in the dispersion medium, in the presence of0.1 to 80 mass parts of a reactive dispersant (D11) with respect to 100mass parts of (A), the reactive dispersant (D11) being an unsaturatedpolyol having a nitrogen-containing bond, which is formed by bonding asubstantially saturated polyol (a) with a monofunctional active hydrogencompound (e) having at least one polymerizable unsaturated group via apolyisocyanate (f), and whose average value of a ratio of a number ofunsaturated groups to a number of nitrogen-containing bonds originatingfrom an NCO group in one molecule of (D11) is 0.1 to 0.4.

[0025] [Eleventh Invention] A method for producing a foamed ornon-foamed urethane resin, comprising reacting a polyol component with apolyisocyanate component in the presence or absence of a blowing agent,wherein the polymer polyol composition according to any one of theabove-described first through fourth and eighth through tenth inventionsis used as at least a part of the polyol component.

DETAILED DESCRIPTION OF THE INVENTION

[0026] In the first invention of the present invention, the content ofthe polymer particles (B) dispersed in (A) in the polymer polyolcomposition (I) is usually from 35 to 75 mass %, preferably from 45 to75 mass %. If the content of (B) is not less than 35 mass %, apolyurethane foam having a sufficient compressive hardness can beobtained. Furthermore, if the content of (B) is not more than 75 mass %,the polymer particles do not aggregate and settle, so that handlingbecomes easy.

[0027] Furthermore, in the first invention, it is necessary that theamount of the soluble polymers (P) dissolved in the polyol (A) in (I) isnot more than 5 mass %, preferably not more than 3 mass %, based on themass of (A). If the amount of (P) exceeds 5 mass %, the viscosity of thepolymer polyol composition increases. As a result, handling becomesdifficult, and a polyurethane foam with a low hardness is produced.

[0028] The soluble polymers (P) dissolved in the polyol (A) herein referto the soluble polymers obtained by removing the polymer particles (B)insoluble in (A) as well as (A) (containing small amounts of by-productsof low molecular weight) from the polymer polyol composition (I), andthey are usually compounds having a higher molecular weight than thepolyol (A).

[0029] The amount of the soluble polymers (P) is measured as follows.

[0030] 20 g of methanol is added to 5 g of (I) and put in a stainlesstube of 100 cc. The polymer particles (B) are allowed to aggregate by acentrifugation at 18,000 rpm for 60 minutes at a temperature of 20° C.to obtain a transparent supernatant. From this solution, methanol isremoved by a pressure-reducing dryer, and then the polyol (A)(containing small amounts of by-products of low molecular weight) andthe polymers (P) soluble in (A) [(P) has a molecular weight of at least4000; in chromatography, the peak of (P) usually appears on the side ofa higher molecular weight than the peak of (A)] are sampled bypreparative liquid chromatography. The amount of (P) is determined fromthe mass ratio of the sampled (A) and (P). The soluble polymers (P)usually have a weight-average molecular weight (measured by gelpermeation chromatography; hereinafter abbreviated as GPC) of 6000 to30000, however, they may include those having a higher molecular weight.

[0031] When the soluble polymers (P) cannot be separated from the polyol(A) by preparative liquid chromatography (when the molecular weights of(P) and (A) overlap), the polymer particles (B) are allowed to aggregateby a centrifugation in the same way as the above to obtain a transparentsupernatant. From this solution, methanol is removed by apressure-reducing dryer, and then diethyl ether is added. The resultingprecipitate is filtered and dried. As a result, the soluble polymers (P)can be separated from (A).

[0032] In the second invention of the present invention, the content ofthe polymer particles (B) in the polymer polyol composition (I) isusually from 35 to 75 mass %, preferably from 45 to 75 mass %. If thecontent of (B) is less than 35 mass %, a polyurethane foam having asufficient compressive hardness cannot be obtained. Furthermore, whenthe content of (B) exceeds 75 mass %, the polymer particles aggregateand settle, so that handling becomes difficult.

[0033] In the second invention, the viscosity V (mPa·s) of the polymerpolyol composition (I) measured by a Brookfield viscosimeter at 25° C.is usually in the range of the inequality (1) below, preferablysatisfying both the inequalities (2) and (3) below:

V≦(Va−Va×C/10){circumflex over ( )}[e{circumflex over ( )}x],  (1)

V≦(Va−Va×C/10){circumflex over ( )}[e{circumflex over ( )}y], and  (2)

V≧0.5×(Va−Va×C/10){circumflex over ( )}[e{circumflex over ( )}y],  (3)

[0034] where x=0.0010354×Bp{circumflex over ( )}1.5,

[0035] y=0.0009514×Bp{circumflex over ( )}1.5,

[0036] Va is a viscosity (mPa·s) of (A) measured by a Brookfieldviscosimeter at 25° C.,

[0037] C is a content of (C) in (I) (mass %),

[0038] Bp is a content of (B) in (I) (mass %),

[0039] symbol {circumflex over ( )} indicates a power, and

[0040] symbol “e” is the base of the natural logarithm.

[0041] The conditions of the measurements of V and Va are as follows:

[0042] 1,500 mPa·s or less; Rotor No. 3, 60 rpm

[0043] 1,500 to 3,000 mPa·s; Rotor No. 3, 30 rpm

[0044] 3,000 to 8,000 mPa·s; Rotor No. 3, 12 rpm

[0045] 8,000 to 16,000 mPa·s; Rotor No. 3, 6 rpm

[0046] 16,000 to 40,000 mPa·s; Rotor No. 4, 12 rpm, and

[0047] 40,000 to 100,000 mPa·s; Rotor No. 4, 6 rpm.

[0048] By satisfying the range of the inequality (1), the polymer polyolcomposition (I) can have good miscibility with other materials and alsogood handling properties.

[0049] In the second invention, a diluent (C) may be used as needed, andit may be contained in the polymer polyol composition so that theviscosity of the polymer polyol composition is decreased. Examples of(C) include internal olefins having 5 to 30 carbon atoms such as hexene,octene and decene; flame retardants with a low viscosity (100 mPa·s/25°C. or lower), e.g. tris(chloroethyl)phosphate andtris(chloropropyl)phosphate; and solvents, e.g. aromatic solvents suchas toluene and xylene.

[0050] The content of (C) in (I) is preferably not more than 3 mass %,more preferably not more than 2 mass %, particularly preferably not morethan 1 mass %. However, as described later, the content of (C) may beadjusted in the foregoing range by using a larger amount of (C) uponpolymerizing the ethylenically unsaturated compound (b) and thereafterremoving (C) after the polymerization by stripping.

[0051] To obtain the polymer polyol composition (I) of the first and/orsecond invention, for example, the following methods (i) and (ii) may beemployed.

[0052] (i) [Fifth Invention] A polymer polyol composition is produced bypolymerizing an ethylenically unsaturated compound (b) in a polyol (A)in the presence or absence of a dispersant (D) and/or a diluent (C),wherein (b) containing at least 5 mass % of an ethylenically unsaturatedcompound (b1) having a number-average molecular weight of at least 500is used.

[0053] (ii) [Sixth Invention] A polymer polyol composition comprising apolyol (A) and polymer particles (B) dispersed in (A) is produced byseparating the polymer particles (B) from a polymer polyol compositionobtained by polymerizing (b) in a polyol, and mechanically dispersingthe polymer particles (B) in (A) not containing more than 5 mass % ofsoluble polymers, based on the mass of (A).

[0054] Furthermore, the following methods (iii) to (v) may be employed.

[0055] (iii) [Method for Obtaining the Polymer Polyol Composition of theEighth Invention] When polymer particles (B) are formed by polymerizingan ethylenically unsaturated compound (b) in the dispersion mediumcomposed of a polyol (A), or (A) and a diluent (C) in the presence orabsence of a dispersant (D), (b) containing at least 5 mass % of aterminal ethylenically-unsaturated group containing compound (b3) havinga number-average molecular weight of 160 to 490 and a solubilityparameter SPb of 9.5 to 13 is used.

[0056] (iv) [Method for Obtaining the Polymer Polyol Composition of theNinth Invention] When polymer particles (B) are dispersed in thedispersion medium, the polymer particles (B) are formed by polymerizingthe ethylenically unsaturated compound (b) in the dispersion mediumcomposed of the polyol (A), or (A) and the diluent (C) in the presenceof a reactive dispersant (D), 0.5 to 50 mass parts of a reactivedispersant (D1) with respect to 100 mass parts of (A) is used as thedispersant (D). Here, the reactive dispersant (D1) is an unsaturatedpolyol having a nitrogen containing bond, which is formed by bonding asubstantially saturated polyol (a) with a monofunctional active hydrogencompound (e) having at least one polymerizable unsaturated group via apolyisocyanate (f).

[0057] (v) [Method for Obtaining the Polymer Polyol Composition of theTenth Invention] When the polymer particles (B) are formed bypolymerizing the ethylenically unsaturated compound (b) in thedispersion medium composed of the polyol (A), or (A) and the diluent (C)in the presence of a reactive dispersant (D), 0.1 to 80 mass parts of areactive dispersant (D11) with respect to 100 mass parts of (A) is usedas the reactive dispersant (D). Here, the reactive dispersant (D11) isan unsaturated polyol having a nitrogen-containing bond, which is formedby bonding a substantially saturated polyol (a) with a monofunctionalactive hydrogen compound (e) having at least one polymerizableunsaturated group via a polyisocyanate (f), whose average value of aratio of a number of unsaturated groups to a number ofnitrogen-containing bonds originating from an NCO group in one moleculeof (D11) is 0.1 to 0.4.

[0058] Among these methods, the methods (i) and (iii) to (v) arepreferred, the methods (iii) to (v) are more preferred, and the method(iii) in combination with the method (iv) or (v) is preferred inparticular.

[0059] The third invention of the present invention is the polymerpolyol composition (II) obtained by the method of the fifth inventionusing a dispersant (D) as an essential component. It is preferable thatthe content of the soluble polymers (P) is not more than 5 mass %, basedon the mass of (A). However, the content also may be not more than 10mass %. Furthermore, in the polymer polyol composition in the eighth totenth inventions, the content of the soluble polymer (P) preferably isnot more than 5 mass % based on the mass of (A), but it may be not morethan 10 mass %, in the case where the dispersant (D) is used.

[0060] As the polyol (A) in the first to third and eighth to tenthinventions, known polyols usually used in the production of polymerpolyols may be employed. For example, compounds (A1) formed by adding analkylene oxide to a compound containing two or more (preferably 2 to 8)active hydrogen atoms (e.g. polyhydric alcohols, polyhydric phenols,amines, polycarboxylic acids and phosphoric acids) and mixtures thereofmay be used.

[0061] Among these, compounds formed by adding an alkylene oxide to apolyhydric alcohol are preferred.

[0062] The polyhydric alcohols include dihydric alcohols having 2 to 20carbon atoms (aliphatic diols, for instance, alkylene glycols such asethylene glycol, diethylene glycol, propylene glycol, 1,3- or1,4-butanediol, 1,6-hexanediol, and neopentylglycol; and alicyclicdiols, for instance, cycloalkylene glycols such as cyclohexanediol andcyclohexanedimethanol); trihydric alcohols having 3 to 20 carbon atoms(aliphatic triols, for instance, alkane triols such as glycerol,trimethylolpropane, trimethylolethane, and hexanetriol, andtriethanolamine); polyhydric alcohols having 4 to 8 hydroxyl groups and5 to 20 carbon atoms (aliphatic polyols, for instance, alkane polyolsand intramolecular or intermolecular dehydration products of the samesuch as pentaerythritol, sorbitol, mannitol, sorbitan, diglycerol, anddipentaerythritol; and saccharides and derivatives of the same such assucrose, glucose, mannose, fructose, and methylglucoside).

[0063] The polyhydric phenols include monocyclic polyhydric phenols suchas pyrogallol, hydroquinone and phloroglucinol; bisphenols such asbisphenol A, bisphenol F and bisphenol sulfone; and condensationproducts of phenols and formaldehyde (novolak).

[0064] The amines include ammonia; and aliphatic amines such as alkanolamines having 2 to 20 carbon atoms (e.g. monoethanolamine,diethanolamine, isopropanolamine and aminoethylethanolamine), alkylamines having 1 to 20 carbon atoms (e.g. n-butylamine and octylamine),alkylene diamines having 2 to 6 carbon atoms (e.g. ethylenediamine,propylenediamine and hexamethylenediamine), and polyalkylene polyamines(from dialkylene triamines to hexaalkylene heptamines having 2 to 6carbon atoms in the alkylene group, e.g. diethylenetriamine andtriethylenetetramine).

[0065] The amines further include aromatic mono- or polyamines having 6to 20 carbon atoms (e.g. aniline, phenylenediamine, tolylenediamine,xylylenediamine, diethyl toluenediamine, methylenedianiline, anddiphenyl ether diamine); alicyclic amines having 4 to 20 carbon atoms(isophoronediamine, cyclohexylenediamine anddicyclohexylmethanediamine); and heterocyclic amines having 4 to 20carbon atoms (e.g. aminoethylpiperazine).

[0066] The polycarboxylic acids include aliphatic polycarboxylic acidshaving 4 to 18 carbon atoms (e.g. succinic acid, adipic acid, sebacicacid, glutaric acid, and azelaic acid), aromatic polycarboxylic acidshaving 8 to 18 carbon atoms (e.g. terephthalic acid and isophthalicacid), and mixtures of two or more thereof.

[0067] As the alkylene oxide added to the active hydrogen-containingcompound, alkylene oxides having 2 to 8 carbon atoms may be used. Thealkylene oxides include ethylene oxide (hereinafter abbreviated as EO),propylene oxide (hereinafter abbreviated as PO), 1,2-, 1,4-, 1-3, or2,3-butylene oxide (hereinafter abbreviated as BO), styrene oxide(hereinafter abbreviated as SO), and the like, and combinations of twoor more thereof (block addition and/or random addition). Preferably, POor a combination of PO and EO (containing not more than 25 mass % of EO)is used. The method for adding the alkylene oxide is not particularlylimited, and examples of the same include known methods employingordinary catalysts such as alkaline catalysts (for instance, KOH).

[0068] Specific examples of the polyol are adducts of PO to the activehydrogen-containing compound, and adducts of PO and other alkylene oxide(hereinafter abbreviated as AO) to the active hydrogen-containingcompounds produced by the following methods, or esterification productsof these adduct compounds with a polycarboxylic acid or phosphoric acid:

[0069] (i) block addition of PO-AO in this order (capped);

[0070] (ii) block addition of PO-AO-PO-AO in this order (balanced);

[0071] (iii) block addition of AO-PO-AO in this order;

[0072] (iv) block addition of PO-AO-PO in this order (active secondary);

[0073] (v) random addition of mixed PO and AO; and

[0074] (vi) random addition or block addition according to the orderdescribed in the specification of U.S. Pat. No. 4,226,756.

[0075] Furthermore, a hydroxyl equivalent of the compound (A1) ispreferably 200 to 4000, more preferably 400 to 3000. Two or more typesof compounds (A1) in combination having a total hydroxy equivalent inthe foregoing range are preferably used as well.

[0076] As the polyol (A), the compounds (A1) formed by adding analkylene oxide to the active hydrogen-containing compound in combinationwith other polyols (A2) may be used. In this case, the ratio of(A1)/(A2) used is preferably from 100/0 to 80/20 by mass.

[0077] Other polyols (A2) include high-molecular polyols such aspolyester polyols and modified polyols, and mixtures thereof.

[0078] The polyester polyols include: condensation reaction products ofthe above described polyhydric alcohols and/or polyether polyols (e.g.dihydric alcohols such as ethylene glycol, diethylene glycol, propyleneglycol, 1,3- or 1,4-butanediol, 1,6-hexanediol and neopentylglycol,mixtures of these dihydric alcohols with polyhydric alcohols havingthree or more hydroxyl groups, such as glycerol and trimethylol propane,and low-mole (1 to 10 moles) alkylene oxide adducts of these polyhydricalcohols) with above described polycarboxylic acids or ester-formingderivatives thereof such as anhydrides thereof or lower alkyl (thenumber of carbon atoms in the alkyl group: 1 to 4) esters thereof (e.g.adipic acid, sebacic acid, maleic anhydride, phthalic anhydride,dimethyl terephthalate, etc.), or with the above-described carboxylicanhydride and alkylene oxide; alkylene oxide (EO, PO, etc.) adducts ofthe condensation reaction products; polylactone polyol, for instance,products obtained by ring-opening polymerization of lactones(ε-caprolactone, etc.) by using the above-described polyhydric alcohol,as an initiator; polycarbonate polyols, for instance, a reaction productof the above-described polyhydric alcohol and alkylene carbonate; andthe like.

[0079] The modified polyols include polydiene polyols such aspolybutadiene polyol, and hydrogenate products of the same;hydroxyl-containing vinyl polymers such as acrylic polyols; polyolsbased on a natural oil, such as castor oil; modification products ofnatural oil-based polyols; and the like.

[0080] These high molecular polyols usually have 2 to 8 hydroxyl groups,preferably 3 to 8 hydroxyl groups, and preferably have a hydroxylequivalent of 200 to 4,000, more preferably 400 to 3,000.

[0081] The number-average molecular weight (according to gel permeationchromatography (GPC); this also applies to the number-average molecularweights described below) of the polyol (A) is usually at least 500,preferably from 500 to 20,000, particularly preferably from 1,200 to15,000, most preferably from 2,000 to 9,000. When the number-averagemolecular weight of the polyol (A) is at least 500, the producedpolyurethane foam is unlikely to be brittle. Furthermore, when thenumber-average molecular weight of (A) is not more than 20,000, theviscosity of (A) is low, and it is desirable in the aspect of thehandling properties of the polymer polyol. Furthermore, the polyol (A)preferably has a hydroxyl equivalent of 200 to 4000, more preferably 400to 3000.

[0082] When the polymer particles (B) are formed by polymerizing (b) inthe sixth invention, the same as those described above for the polyol(A) also can be used. The polyol and (A) may be either the same ordifferent.

[0083] The dispersant (D) used in the third, fifth, and eighthinventions is not particularly limited, and conventional dispersantsused in polymer polyols can be employed. Two or more kinds of thedispersants (D) may be employed in combination.

[0084] Examples of (D) include: (i) macromer-type dispersants obtainedby reacting a polyol with an ethylenically unsaturated compound, such asa modified polyether polyol containing a vinyl group, which is obtainedby reacting at least a part of hydroxyl groups of a polyol having aweight-average molecular weight of 500 to 10000 with methylene dihalideand/or ethylene dihalide so as to have a high molecular weight, andfurther reacting the obtained reaction product with a vinylgroup-containing compound such as a (meth)acrylic acid or a derivativeof the same [e.g., glycidyl (meth)acrylate], or maleic acid or maleicanhydride, and which has a weight-average molecular weight of twice tosix times the weight-average molecular weight of the polyol (e.g. see JP08(1996)-333508 A); (ii) graft-type dispersants obtained by combining apolyol with an oligomer, such as a graft polymer having two or moresegments with an affinity for polyols as side chains, in which thedifference between the solubility parameter of the side chains and thesolubility parameter of a polyol is not more than 1.0 (e.g., polyoxyalkylene ether groups having a number average molecular weight of 88 to750), and having a segment with an affinity for polymers as a mainchain, in which the difference between the solubility parameter of themain chain and the solubility parameter of a polymer formed from a vinylmonomer is not more than 2.0 (e.g., vinyl-based polymers having a numberaverage molecular weight of 1000 to 30000) (e.g. see JP 05(1993)-059134A); (iii) high molecular polyol type dispersants, e.g. a modified polyolobtained by reacting at least a portion of the hydroxyl groups in apolyol having an average molecular weight of 500 to 10000 with amethylene dihalide and/or an ethylene dihalide to increase its molecularweight to twice to six times the average molecular weight of the polyol(e.g. see JP 07(1995)-196749 A); (iv) oligomer type dispersants, e.g. avinyl oligomer with a weight-average molecular weight of 1,000 to30,000, at least a portion of which being soluble in polyols (e.g.,acrylonitrile/styrene copolymer), and a dispersant comprising thisoligomer and the vinyl group-containing modified polyether polyoldescribed for (i) above (e.g. see JP 09(1997)-77968 A); and the like.Among these, the types (i) and (iv) are preferred. In any case, it ispreferable that (D) has a number-average molecular weight (according toGPC) of 1,000 to 10,000.

[0085] Furthermore, the amount of (D) used in the case where such aconventional dispersant is used as (D) is preferably not more than 15mass %, more preferably not more than 10 mass %, particularly preferablyfrom 0.1 to 8 mass %, based on the mass of (b).

[0086] Apart from these conventional dispersants, reactive dispersants(D1) in the ninth and tenth inventions (including (D11)), which will bedescribed later, may be used as the dispersant (D), and they areparticularly preferred.

[0087] The reactive dispersant (D1) is an unsaturated polyol having anitrogen-containing bond, which is formed by bonding a substantiallysaturated polyol (a) with a monofunctional active hydrogen compound (e)having at least one polymerizable unsaturated group via a polyisocyanate(f). Here, “substantially saturated” means that an unsaturation degreemeasured by the method specified in JIS K-1557 is not more than 0.2meq/g (preferably not more than 0.08 meq/g).

[0088] As the polyol (a) composing the reactive dispersant (D1), thosementioned as the polyol (A) can be used. The polyols (a) and (A) may bethe same, or may be different.

[0089] The number of hydroxyl groups in one molecule of the polyol (a)is at least two, preferably two to eight, more preferably three to four.The hydroxyl equivalent of the polyol (a) is preferably 1000 to 3000,more preferably 1500 to 2500.

[0090] The compound (e) used for obtaining (D1) is a compound having oneactive hydrogen-containing group and at least one polymerizableunsaturated group. Examples of the active hydrogen-containing groupinclude a hydroxyl group, an amino group, an imino group, a carboxylgroup, an SH group, etc., among which the hydroxyl group is preferred.

[0091] The polymerizable unsaturated group of the compound (e)preferably has a polymerizable double-bond, and the number of thepolymerizable unsaturated groups in one molecule is preferably one tothree, more preferably one. More specifically, preferred as the compound(e) is an unsaturated monohydroxy compound having one polymerizabledouble bond.

[0092] Examples of the foregoing unsaturated monohydroxy compoundinclude, for instance, monohydroxy-substituted unsaturated hydrocarbons,monoesters of unsaturated monocarboxylic acids and dihydric alcohols,monoesters of unsaturated dihydric alcohols and monocarboxylic acids,phenols having alkenyl side chain groups, and unsaturated polyethermonools.

[0093] Examples of the monohydroxy-substituted unsaturated hydrocarboninclude: alkenol having 3 to 6 carbon atoms such as (meth)allyl alcohol,2-butene-1-ol, 3-butene-2-ol, 3-butene-1-ol, etc.; and alkynol, forinstance, propargyl alcohol.

[0094] Examples of the monoesters of unsaturated monocarboxylic acidsand dihydric alcohols include monoesters of: unsaturated monocarboxylicacids each having 3 to 8 carbon atoms, for instance, acrylic acid,methacrylic acid, chrotonic acid, or itaconic acid; and theabove-described dihydric alcohols (dihydric alcohols having 2 to 12carbon atoms such as ethylene glycol, propylene glycol, and butyleneglycol). Specific examples of the foregoing monoesters include 2-hydroxyethyl acrylate, 2-hydroxy ethyl methacrylate, 2-hydroxy propyl acrylate,2-hydroxy propyl methacrylate, 2-hydroxy butyl acrylate, 4-hydroxy butylacrylate, etc.

[0095] Examples of the monoesters of unsaturated dihydric alcohols andmonocarboxylic acids include monoesters of unsaturated dihydric alcoholshaving 3 to 8 carbon atoms and monocarboxylic acids having 2 to 12carbon atoms, for instance, acetic acid monoester of butene diol.

[0096] Examples of the phenol having an alkenyl side chain group includephenols each having an alkenyl side chain group having 2 to 8 carbonatoms, such as oxystyrene, hydroxy-a-methyl styrene, etc.

[0097] Examples of the unsaturated polyether monool include 1 to 50-molealkylene oxide (having 2 to 8 carbon atoms) adducts of themonohydroxy-substituted unsaturated hydrocarbon or the phenol having thealkenyl side chain group (for instance, polyoxyethylene (having a degreeof polymerization of 2 to 10) monoallyl ether).

[0098] The examples of the compound (e) other than the unsaturatedmonohydroxy compound include the following:

[0099] Examples of the compound (e) having an amino group or an iminogroup include mono- and di-(meth)allyl amine, amino alkyl (having 2 to 4carbon atoms) (meth)acrylate [e.g., amino ethyl (meth)acrylate], andmonoalkyl (having 1 to 12 carbon atoms) amino alkyl (having 2 to 4carbon atoms) (meth)acrylate [e.g., monomethyl aminoethyl-methacrylate]; examples of the compound (e) having a carboxylgroup include the aforementioned unsaturated monocarboxylic acids; andexamples of the compound (e) having an SH group include compoundscorresponding to the aforementioned unsaturated monohydroxy compounds(in which SH substitutes for OH).

[0100] Examples of the compound (e) having not less than twopolymerizable double bonds include poly(meth)allylethers of theaforementioned polyhydric alcohols having a valence of 3, 4 to 8, ormore, or polyesters of the above alcohols with the aforementionedunsaturated carboxylic acids [e.g., trimethylol propane diallylether,pentaerythritol triallylether, glycerol di(meth)acrylate, etc.]

[0101] Among these compounds, preferred are the alkenols having 3 to 6carbon atoms, the monoesters of unsaturated monocarboxylic acids having3 to 8 carbon atoms and dihydric alcohols having 2 to 12 carbon atoms,and the phenols having alkenyl side chain groups. More preferred aremonoesters of (meth)acrylic acids with ethylene glycol, propyleneglycol, or butylene glycol; allyl alcohol; and hydroxy a-methyl styrene.Particularly preferred are 2-hydroxy ethyl (meth)acrylate.

[0102] Furthermore, though the molecular weight of (e) is notparticularly limited, it is preferably not more than 1000, particularlypreferably not more than 500.

[0103] The polyisocyanate (f) is a compound having at least twoisocyanate groups, and examples of the same include aromaticpolyisocyanates, aliphatic polyisocyanates, alicyclic polyisocyanates,araliphatic polyisocyanates, modification products of thesepolyisocyanates (modification products having an urethane group, acarbodiimido group, an allophanate group, an urea group, a biuret group,an isocyanurate group, or an oxazolidon group, etc.), and mixtures oftwo or more of these.

[0104] Examples of the aromatic polyisocyanates include aromaticdiisocyanates having 6 to 16 carbon atoms (excluding those contained inNCO groups; this applies to the polyisocyanates mentioned below),aromatic triisocyanates having 6 to 20 carbon atoms, crude products ofthese isocyanates, etc. More specifically, the examples include 1,3- and1,4-phenylene diisocyanates, 2,4- and/or 2,6-tolylene diisocyanates(TDI), crude TDI, 2,4′- and/or 4,4′-diphenyl methane diisocyanate (MDI),crude MDI [products of crude diaminodiphenyl methane with phosgene wherethe crude diaminodiphenyl methane is a condensation product offormaldehyde with aromatic amine (aniline) or a mixture of the same; oris a mixture of diaminodiphenyl methane and a small amount (e.g., 5 to20 mass %) of a polyamine having three or more functional groups;polyallyl polyisocyanate (PAPI), etc.], naphthylene-1,5-diisocyanate,triphenyl methane-4,4′, 4″-triisocyanate, etc.

[0105] Examples of aliphatic polyisocyanates include aliphaticdiisocyanates having 2 to 18 carbon atoms. More specifically, theexamples include 1,6-hexamethylene diisocyanate,2,2,4-trimethylhexamethylene diisocyanate, lysine diisocyanate, etc.

[0106] Examples of alicyclic polyisocyanates include alicyclicdiisocyanates having 4 to 16 carbon atoms. More specifically, theexamples include isophorone diisocyanate, 4,4-dicyclohexyl methanediisocyanate, 1,4-cyclohexane diisocyanate, norbornane diisocyanate,etc.

[0107] Examples of araliphatic isocyanates include araliphaticdiisocyanates having 8 to 15 carbon atoms. More specifically, theexamples include xylylene diisocyanate, α,α,α′,α′-tetramethyl xylylenediisocyanate, etc.

[0108] Examples of modified polyisocyanates include urethane-modifiedMDI, carbodiimide-modified MDI, sucrose-modified TDI, castoroil-modified MDI, etc.

[0109] Among these, aromatic diisocyanates are preferred, and 2,4-and/or 2,6-TDI is more preferred.

[0110] The nitrogen-containing bond of the reactive dispersant (D1) isgenerated by reaction of the isocyanate group with an activehydrogen-containing group. In the case where the activehydrogen-containing group is a hydroxy group, an urethane bond isgenerated principally, while in the case where it is an amino group, anurea bond is generated principally. An amide bond is generated in thecase of a carboxyl group, while a thiourethane group is generated in thecase of a SH group. In addition to these groups, another bond, forinstance, a biuret bond, an allophanate bond, etc., may be generated.

[0111] These nitrogen-containing bonds are generally classified into twokinds; those generated by reaction of a hydroxy group of the saturatedpolyol (a) with an isocyanate group of the polyisocyanate (f); and thosegenerated by reaction of an active hydrogen-containing group of theunsaturated monofunctional active hydrogen compound (e) with anisocyanate group of (f).

[0112] From a viewpoint of the dispersion stability of the polymerpolyol, an average of the number of the hydroxy groups in one moleculeof (D1) is usually not less than 2, preferably 2.5 to 10, morepreferably 3 to 7. An average of the number of the unsaturated groups inone molecule of (D1) is preferably 0.8 to 2, more preferably 0.9 to 1.2.

[0113] Furthermore, from the viewpoint of the dispersion stability, ahydroxyl equivalent of (D1) is preferably 500 to 10000, more preferably1000 to 7000, particularly preferably 2000 to 6000.

[0114] Furthermore, from the viewpoint of the dispersion stability andease of handling of the polyol, (D1) preferably has a number averagemolecular weight (in end-group analysis) of 5000 to 40000, morepreferably 10000 to 30000, particularly preferably 15500 to 25000.

[0115] Furthermore, (D1) preferably has a viscosity of 10000 to 50000mPa·s/25° C., more preferably 12000 to 48000 mPa·s/25° C., particularlypreferably 15000 to 35000 mPa·s/25° C. In the case where the viscosityis in the foregoing range, the polymer has better dispersibility,thereby causing the polymer polyol obtained with use of (D1) to have alower viscosity and providing more ease of handling.

[0116] The method for producing the reactive dispersant (D1) byemploying these materials is not particularly limited.

[0117] Examples of preferable methods include a method of adding apolyisocyanate (f) to a mixture of an unsaturated monofunctional activehydrogen compound (e) and a substantially saturated polyol (a) andreacting the same in the presence of a catalyst as needed, and a methodof reacting (e) and (f) in the presence of a catalyst as needed toproduce an unsaturated compound having an isocyanate group and reactingthe same with (a). The latter method is most preferred since the methodprovides an unsaturated polyol having a nitrogen-containing bond, fromwhich a minimum of by-products such as compounds having no hydroxy groupare generated.

[0118] Alternatively, (D1) may be formed by a method in which, in placeof (e) or (a), a precursor of the same is reacted with (f) andthereafter the precursor portion is modified [e.g., after reacting theaforementioned precursor with isocyanate, the obtained reaction productis reacted with an unsaturated monocarboxylic acid or an ester-formingderivative of the same so as to introduce an unsaturated group, or afterreacting the aforementioned precursor with isocyanate, the obtainedreaction product is coupled using alkylene dihalide, or dicarboxylicacid, so as to form (D1)].

[0119] Examples of the catalyst for the foregoing reaction includeconventionally used urethane catalysts such as tin-based catalysts(dibutyltin dilaurate, stannous octoate, etc.), other metal-basedcatalysts (tetrabutyl titanate, etc.), amine-based catalyst (triethylenediamine, etc.). Among these, tetrabutyl titanate is preferred.

[0120] An amount of the catalyst is preferably 0.0001 to 5 mass %, morepreferably 0.001 to 3 mass %, based on the mass of a reaction mixture.

[0121] As to the reaction ratio of these three components, an equivalentratio of the active hydrogen-containing groups of (e) and (a) to theisocyanate groups of (f) is preferably (1.2 to 4):1, more preferably(1.5 to 3):1 based on a total amount of the components used in thereaction.

[0122] Furthermore, an amount of (e) used in the reaction is preferablyless than 2 parts by mass (mass parts), more preferably 0.5 to 1.8 massparts, with respect to 100 mass parts of (a).

[0123] It should be noted that the following method may be used: amixture of (D1) and (a) is formed using a significantly excessive amountof (a) for reaction with (f), and unreacted (a) is not separated but isused as it is, as a part of the polyol (A).

[0124] The reactive dispersant (D1) obtained by the foregoing methodsmay be a single compound, but in many cases it is a mixture of variouscompounds such as those expressed by a general formula (5) shown below:

[0125] where:

[0126] z represents a residue of (f) having a valence of h (h is aninteger of not less than 2);

[0127] T represents a residue of (e) (having a polymerizable unsaturatedgroup);

[0128] A₁ represents a residue of a polyol having a valence of q₁ [OHprepolymer derived from (a), or (a) and (f)], and A₂ represents aresidue of a polyol having a valence of q₂ [OH prepolymer derived from(a), or (a) and (f)] (q₁ and q₂ are integers of not less than 2); and

[0129] X represents a single bond, O, S, or

[0130] where:

[0131] T′ represents H or an alkyl group having 1 to 12 carbon atoms;

[0132] q₁−g≧0;

[0133] g represents an integer of not less than 1;

[0134] j represents an integer of not less than 1:

[0135] h−j−1≧0; and

[0136] the total number of OH groups is not less than 2.

[0137] In other words, the reactive dispersant (D1) includes one polyol(a) and one compound (e) that are bonded with each other via onepolyisocyanate (f), a plurality of compounds (e) and one polyol (a) thatare bonded with each other via one polyisocyanate (f) for each (e),polyols (a) and compounds (e), not less than three in total, that arebonded with each other via a plurality of polyisocyanates (f), etc.Furthermore, in addition to these, a plurality of polyols (a) bondedwith each other via polyisocyanates (f) (a polyol having no unsaturatedgroup, which contains a nitrogen-containing bond) and a plurality ofcompounds (e) bonded with each other via polyisocyanates (f) (anunsaturated compound having no hydroxyl group, which contains anitrogen-containing bond) may be formed as by-products, and also, thereactive dispersant (dl) may contain unreacted (a) and (e) in somecases.

[0138] These mixtures may be used as dispersants without anymodification, but those containing a minimum of polyols having nounsaturated group, which contain a nitrogen-containing bond, orunsaturated compounds having no hydroxyl group, which contain anitrogen-containing bond, are preferred, and they may be used afterremoving the impurities that are removable.

[0139] Furthermore, since unsaturated groups in (D1) are present atterminals or in the vicinity of terminals of molecular chains of thepolyol, they are polymerizable with monomers.

[0140] A dispersant (D11) used in the tenth invention is obtained byreacting (a), (e), and (f) so that K, indicative of an average of aratio of the number of unsaturated groups to the number ofnitrogen-containing bonds originating from NCO groups in one molecule of(f), which is derived according to a formula (4), is 0.1 to 0.4:

K=[number of moles of (e)×number of unsaturated groups of (e)]/[numberof moles of (f)×number of NCO groups of (f)]  (4)

[0141] The value of K is more preferably 0.1 to 0.3, particularlypreferably 0.2 to 0.3. In the case where the value of K is in theforegoing range, a particularly excellent dispersion stability ofpolymer polyol can be obtained.

[0142] As to the composition ratio of a polyol (A) and a reactivedispersant (D1) when a polymer polyol is formed, 0.5 to 50 mass parts of(D1) is preferably used with respect to 100 mass parts of (A) [NinthInvention]. More preferably 0.8 to 15 mass parts, or particularlypreferably 1 to 10 parts, of (D1) is used with respect to 100 parts of(A). With not more than 50 mass parts of (D1), the viscosity of thepolymer polyol does not increase, while with not less than 0.5 massparts, an excellent dispersibility is obtained.

[0143] In the case of (D11), since it is excellent in dispersionstability, the ratio of use of the same can be varied in a wide range[for instance, 0.1 to 80 mass parts with respect to 100 mass parts of(A)], but the ratio is preferably in the foregoing range.

[0144] The reactive dispersants (D1) and (D11) of the ninth and tenthinventions can be used for producing conventional polymer polyolcompositions in which only (b2) that will be described later is used asan ethylenically-unsaturated compound, since a polymer polyolcomposition obtained by using the dispersant (D1) or (D11) has excellentdispersion stability. However, these dispersants are particularlypreferably used for producing a polymer polyol composition in which aspecific ethylenically unsaturated group-containing compound (b1) or(b3) that will be described later are used.

[0145] In the method (i) [Fifth Invention] to obtain the polymer polyolcomposition (I) of the first and/or second inventions and the polymerpolyol composition (II) of the third invention, an ethylenicallyunsaturated compound (b1) having a number-average molecular weight of atleast 500 and an ethylenically unsaturated compound (b2) having anumber-average molecular weight of less than 500 and usually used in theproduction of polymer polyol compositions may be used as theethylenically unsaturated compound (b). Examples of (b2) includearomatic hydrocarbon monomers (b2-1), unsaturated nitrites (b2-2),(meth)acrylic acid esters (b2-3), and other ethylenically unsaturatedcompounds (b2-4), and mixtures of two or more thereof.

[0146] The number-average molecular weight of the ethylenicallyunsaturated compound (b1) is usually at least 500, preferably at least550, particularly preferably from 800 to 10,000, most preferably from1,000 to 10,000. By using (b1) having a number-average molecular weightof at least 500, a polymer polyol having a smaller amount ofpolyol-soluble oligomers can be produced.

[0147] Furthermore, the ethylenically unsaturated compound (b1) can haveone or more double bonds on average. It is preferable that (b1) has from1 to 500 double bonds, more preferably from 1 to 70 double bonds. Byletting (b1) have one or more double bonds, the amount of componentssoluble in polyols can be decreased, and an increase in the viscosity ofthe polymer polyol obtained can be prevented. Moreover, the polyurethaneresin produced using such a compound can be prevented from havingdeteriorated properties.

[0148] Furthermore, when (b1) has two or more double bonds, preferablythe double bonds are non-conjugated.

[0149] Furthermore, it is preferable that the molecular weight (X) perone double bond of (b1) is usually not more than 1200, preferably notmore than 1150, more preferably from 100 to 1050. When (X) is not morethan 1200, a great effect is exhibited to decrease the amount of thepolyol-soluble oligomers in the polymer polyol produced using (b1).

[0150] The molecular weight (X) per one double bond of (b1) is definedby the equation

X=1000/N,

[0151] where N is an unsaturation degree of (b1) measured by the methodspecified in JIS K-1557.

[0152] It is preferable that the ethylenically unsaturated compound (b1)has an ester bond, amide bond, urethane bond, urea bond and/or imidebond, etc. in the molecule. Among these, ester bond, amide bond and/orurethane bond are preferred, and ester bond is particularly preferred.Also, a combination of two or more of these bonds can be present in thesame molecule.

[0153] The ester bond can be formed by (i) a reaction of a carboxylicacid or an acid anhydride with a hydroxyl-containing compound or analkylene oxide, or (ii) a ring-opening reaction of a lactone. The amidebond can be formed by (i) a reaction of a carboxylic acid or an acidanhydride with an amino-containing compound, (ii) a ring-openingreaction of a lactam, or (iii) a polycondensation reaction of anaminocarboxylic acid. The imide bond can be formed by reacting an acidwith diamine to form a polyamic acid and then carrying out a dehydrationreaction. The urethane bond or urea bond can be formed by reacting anisocyanate compound with an active hydrogen-containing compound.

[0154] Examples of the carboxylic acids for forming the ester bond andamide bond include unsaturated aliphatic monocarboxylic acids having 3to 24 carbon atoms, e.g. acrylic acid, methacrylic acid, oleic acid andlinoleic acid; unsaturated aliphatic dicarboxylic acids having 4 to 24carbon atoms, e.g. maleic acid, fumaric acid, itaconic acid andcitraconic acid; saturated aliphatic polycarboxylic acids having 2 to 24carbon atoms, e.g. oxalic acid, malonic acid, succinic acid, glutamicacid, adipic acid, sebacic acid, hexanetricarboxylic acid andhexanetetracarboxylic acid; aromatic polycarboxylic acids having 8 to 24carbon atoms, e.g. isophthalic acid and terephthalic acid; alicyclicdicarboxylic acids having 7 to 24 carbon atoms, e.g.1,4-cyclohexanedicarboxylic acid and tetrahydrophthalic acid;unsaturated carboxylic acid (co)polymers (number-average molecularweight of 1,000 to 10,000), e.g. poly(meth)acrylic acid, polyitaconicacid, copolymers of (meth)acrylic acid and maleic acid, and copolymersof (meth)acrylic acid and styrene; and the like. The term “(meth)acryl-”herein refers to “acryl-” and/or “methacryl-”.

[0155] Examples of the acid anhydride for forming the ester bond oramide bond include aliphatic carboxylic acid anhydrides such as maleicanhydride, itaconic anhydride and citraconic anhydride; and aromaticcarboxylic acid anhydrides such as phthalic anhydride.

[0156] Examples of the hydroxyl-containing compound for forming theester bond include the above (A1) and (A2); polyhydric alcohols andpolyhydric phenols among the active hydrogen-containing compoundsdescribed for the polyol (A); unsaturated alcohols (r) having 3 to 24carbon atoms, e.g. allyl alcohol and propenyl alcohol; (poly)oxyalkyleneethers (C₂-C₈ in the alkylene group; polymerization degree n=1 to 30, nherein refers to the polymerization degree of the (poly)oxyalkylenesegment) of unsaturated alcohols (C3-C₂₄, e.g. (poly)oxypropylene (n=1to 30) monoallyl ether, and (poly)oxybutylene (n=1 to 20) monopropenylether; and polyol polymers such as polyvinyl alcohols (saponificationvalue 70 to 100; number-average molecular weight of 1,000 to 10,000).Examples of the alkylene oxide include those having 2 to 8 carbon atoms,e.g. ethylene oxide, propylene oxide, butylene oxide, and styrene oxide(hereinafter abbreviated as SO), and combinations of two or more thereof(block addition and/or random addition), and the like.

[0157] Example of the lactone for forming the ester bond include thosehaving 5 to 12 carbon atoms, such as caprolactone, enantholactone,laurolactone and undecanolactone.

[0158] Examples of the active hydrogen-containing compound for formingthe amide bond include the amines among the active hydrogen-containingcompounds described for the polyol (A).

[0159] Example of the lactam for forming the amide bond include thosehaving 5 to 12 carbon atoms, such as caprolactam, enantholactam,laurolactam and undecanolactam.

[0160] Examples of the aminocarboxylic acid for forming the amide bondinclude aminocarboxylic acids having 2 to 18 carbon atoms, e.g. aminoacids such as glycine, alanine, valine, leucine, isoleucine andphenylalanine, ω-aminocaproic acid, ω-aminoenanthic acid,ω-aminocaprylic acid, ω-aminopelargonic acid, ω-aminocapric acid,11-aminoundecanoic acid, and 12-aminododecanoic acid, and the like.

[0161] As the acid and diamine used for forming the imide bond, knownacids and diamines used in the synthesis of general polyimide resins maybe employed. Examples of the acid include aromatic tetracarboxylic acidshaving 10 to 20 carbon atoms, such as 3,4,3′,4′-biphenyltetracarboxylicacid, 2,3,3′,4′-biphenyltetracarboxylic acid and pyromellitic acid,anhydrides of these acids, and ester compounds of these acids.Furthermore, examples of the diamine include aromatic diamines having 6to 18 carbon atoms such as 4,4′-diaminodiphenyl ether,p-phenylenediamine, m-phenylenediamine, and 4,4′-diaminodiphenylmethane,and the like.

[0162] As the isocyanate compound for forming the urethane bond or ureabond, known isocyanate compounds used in the synthesis of generalpolyurethane resins can be employed. Examples of the isocyanate compoundinclude those mentioned above as examples of the polyisocyanate (f).

[0163] As the active hydrogen-containing compound for forming theurethane bond or urea bond, the active hydrogen-containing compoundsdescribed above for (A1), (A2) and the polyol (A) above can be employed.

[0164] In (b1) used in the method of the present invention, the esterbond, amide bond, urethane bond, urea bond, or imide bond can beobtained by a conventional reaction of esterification, amidation,urethanation, ureation or imidation.

[0165] For example, the ester bond or amide bond can be formed byputting a carboxylic acid or acid anhydride and an activehydrogen-containing compound in a reaction vessel in predeterminedamounts, and causing a dehydration reaction at 50 to 250° C. Thedehydration reaction can be carried out under reduced pressure, or underatmospheric pressure or increased pressure. Furthermore, the ester bondalso can be obtained by an addition reaction of a carboxylic acid oracid anhydride with an alkylene oxide.

[0166] The ratio [equivalent ratio] of the carbonyl groups of thecarboxylic acid or the acid anhydride to the active hydrogen atoms ofthe active hydrogen-containing compound is usually from 0.01:1 to0.98:1, preferably from 0.1:1 to 0.8:1.

[0167] Known esterification catalysts can be used in the aboveesterification and amidation. Examples of the catalysts includeantimony-based catalysts such as antimony tetraoxide; tin-basedcatalysts such as monobutyl tin oxide; titanium-based catalysts such astetrabutyl titanate; zirconium-based catalysts such as tetrabutylzirconate; metal acetate-based catalysts such as zirconyl acetate andzinc acetate; and combinations of two or more thereof. The amount of thecatalyst used is usually from 0.1 to 5 mass %, based on the total massof the carboxylic acid and the active hydrogen-containing compound.

[0168] Other than the above method, the amide bond also can be formed byputting a predetermined amount of lactam into a reaction vessel andcausing a ring-opening reaction at 50 to 250° C., or by putting apredetermined amount of aminocarboxylic acid into a reaction vessel andcausing a polycondensation reaction at 50 to 250° C.

[0169] The imide bond can be formed by reacting an acid with a diamineat 60 to 130° C. using an organic polar solvent, such asN-methyl-2-pyrrolidone, N,N-dimethylformamide, N,N-dimethylacetoamide orN,N-dimethylsulfoxide, thereby to synthesize an amic acid, anddehydrating it at 60 to 400° C. A catalyst can be added to acceleratethe imidation reaction. Specific examples of the catalyst include basiccompounds such as triethylamine and 2-methylimidazol. The amount of thecatalyst is usually from 0.01 to 5 mass %, based on the total mass ofthe acid and the diamine.

[0170] The urethane bond or urea bond can be formed by putting anisocyanate compound and an active hydrogen-containing compound in areaction vessel in predetermined amounts and reacting at 25 to 150° C.The isocyanate index [equivalent ratio of (NCO groups/active hydrogenatom-containing groups)×100] is usually from 80 to 140, preferably from85 to 120, particularly preferably from 95 to 115.

[0171] When carrying out a urethanation reaction, a conventionalcatalyst for urethane polymerization can be used to accelerate thereaction. Examples of the catalyst include amine-based catalysts such astertiary amines including triethylenediamine and N-ethylmorpholine;tin-based catalysts such as stannous octoate and dibutyl tin dilaurate;other metal catalysts such as lead octoate; and the like. The amount ofthe catalyst is usually from 0.001 to 5 mass %, based on the mass of theisocyanate compound and the active hydrogen compound.

[0172] Specific examples of the ethylenically unsaturated compound (b1)in the method of the present invention are as follows.

[0173] Examples of (b1) having one double bond in the molecule includeunsaturated aliphatic dicarboxylic acid (C₄-C₂₄) diesters of aliphaticalcohol (C₁-C₂₄) (poly)oxyalkylene (C₂-C₈ in the alkylene group) ethers,e.g. maleic acid diesters of polyoxypropylene (n=4 to 30) monomethylethers, fumaric acid diesters of polyoxypropylene (n=3 to 30) monobutylethers, and itaconic acid diesters of random adducts of butanolpolyoxybutylene (n=2 to 20)-polyoxyethylene (n=2 to 10); aliphaticalcohol (C₁-C₂₄) polyoxyalkylene (C₂-C₈ in the alkylene group) ether(meth)acrylates, e.g. polyoxypropylene [n=8(7) to 30] monomethyl ether(meth)acrylates [the numerical value in the parenthesis for n shows thecase of methacrylate; this also applies to the following],polyoxybutylene [n=6(5) to 20] monobutyl ether (meth)acrylates, andpolyoxypropylene (n=5 to 30) monolauryl ether (meth)acrylates;polyoxyalkylene (C₂-C₈ in the alkylene group) ethers of unsaturatedalcohols (C₃-C₂₄), e.g. polyoxypropylene (n=4 to 30) monooleyl ethers,polyoxypropylene (n=8 to 30) monoallyl ethers; unsaturated aliphaticmonocarboxylic acid (C₃-C₂₄) polyoxyalkylene (C₂-C₈ in the alkylenegroup) esters, e.g. random adducts of oleic acid propylene oxide (n=2 to30)-ethylene oxide (n=2 to 10) having a number-average molecular weightof at least 500; and the like.

[0174] Examples of (b1) having two double bonds in the molecule includepolyalkylene (C₂-C₈ in the alkylene group) glycol di(meth)acrylates,e.g. polypropylene glycol [n=7(6) to 30] di(meth)acrylates, andpolybutylene glycol [n=6(5) to 20] di(meth)acrylates; aliphaticcarboxylic acid (C₂-C₂₄) diesters of unsaturated alcohols (C₃-C₂₄), e.g.succinic acid diesters of polyoxypropylene (n=3 to 30) monoallyl ethers,adipic acid diesters of polyoxypropylene (n=3 to 30) monoallyl ethers,succinic acid diesters of polyoxypropylene (n=3 to 30) monopropenylethers; and the like.

[0175] Examples of (b1) having three double bonds in the moleculeinclude unsaturated fatty acid (C₃-C₂₄) triesters of trihydric alcohols(C₃-C₁₂), e.g. tri(meth)acrylates of glycerol polyoxypropylene [n=5(4)to 30] ethers, tri(meth)acrylates of trimethylolpropane polyoxypropylene[n=4(3) to 30] ethers, tri(meth)acrylates of pentaerythritolpolyoxypropylene [n=4(3) to 30] ethers, tri(meth)acrylates of diglycerolpolyoxypropylene (n=3 to 30) ethers, and sorbitan polyoxybutylene[n=3(2) to 20] tri(meth)acrylates; aliphatic carboxylic acid (C₃-C₂₄)triesters of unsaturated alcohols (C₃-C₂₄), e.g. hexanetricarboxylicacid triesters of allyl alcohol (poly)oxypropylene (n=1 to 30) ethers;unsaturated alkyl-containing ether compounds, e.g. triallyl ethers ofglycerol polyoxypropylene (n=5 to 30) ethers; and the like.

[0176] Examples of (b1) having four double bonds in the molecule includeunsaturated fatty acid (C₃-C₂₄) polyesters of polyhydric (4 to 8 or morehydroxyl groups) alcohols, e.g. polyglycerol (n=3 to 4)poly(meth)acrylates having a number-average molecular weight of at least500, polyglycerol (n=2 to 4) polyolates having a number-averagemolecular weight of at least 500, dipentaerythritol poly(meth)acrylateshaving a number-average molecular weight of at least 500, polyglycerol(n=2 to 4) (poly)oxypropylene (n=1 to 30) poly(meth)acrylates having anumber-average molecular weight of at least 500, tetra(meth)acrylates ofpentaerythritol polyoxypropylene [n=3(2) to 30] ethers,tetra(meth)acrylates of sorbitan polyoxybutylene (n=2 to 20) ethers, andpolyvinyl alcohol (saponification value of 70 to 100; number-averagemolecular weight of 1,000 to 10,000) (meth)acrylates; polycarboxylicesters (number-average molecular weight of 1,000 to 10,000) ofunsaturated alcohols (C₃-C₂₄), e.g. hexane tetracarboxylic acid estersof allyl alcohol (poly)oxypropylene (n=1 to 30) ethers, polyesters(number-average molecular weight of 1,000 to 10,000) of (meth)acrylicacid polymers and allyl alcohols, and polyesters (number-averagemolecular weight of 1,000 to 10,000) of maleic acid polymers and allylalcohols; unsaturated alkyl-containing ether compounds, e.g.tetraglycerol polyallyl ethers having a number-average molecular weightof at least 500, and polyallyl ethers of polyglycerol (n=2 to 4)(poly)oxypropylene (n=1 to 30) ethers having a number-average molecularweight of at least 500; polyesters (number-average molecular weight of500 to 10,000) of unsaturated carboxylic acids (C₄-C₂₂) and glycols,e.g. polyesters (number-average molecular weight of 500 to 10,000) ofmaleic acid and ethylene glycol, polyesters (number-average molecularweight of 500 to 10,000) of maleic acid and diethylene glycol,polyesters (number-average molecular weight of 500 to 10,000) of maleicacid and propylene glycol, polyesters (number-average molecular weightof 500 to 10,000) of maleic acid and 1,3- or 1,4-butanediol, polyesters(number-average molecular weight of 500 to 10,000) of itaconic acid andethylene glycol, polyesters (number-average molecular weight of 500 to10,000) of itaconic acid and diethylene glycol, polyesters(number-average molecular weight of 500 to 10,000) of maleic acid andpolyoxypropylene glycol (n=1 to 30), polyesters (number-averagemolecular weight of 500 to 10,000) of itaconic acid and polyoxypropyleneglycol (n=1 to 30), and polyesters (number-average molecular weight of500 to 10,000) of fumaric acid and polyoxybutylene glycol (n=1 to 20);and the like.

[0177] Among these, ester compounds formed from an unsaturatedcarboxylic acid (p) and a glycol (q) and/or ester compounds formed froman unsaturated alcohol (r) and a carboxylic acid (s) are preferred.Particularly, radically polymerizable compounds formed from anunsaturated carboxylic acid (p) and a glycol (q) are preferred. Theunsaturated carboxylic acid (p) is a carboxylic acid having double bonds(non-conjugated in the case of two or more double bonds) in the moleculeor a derivative thereof, e.g. a carboxylic acid having 3 to 24 carbonatoms, such as acrylic acid, methacrylic acid, maleic acid, fumaricacid, itaconic acid, citraconic acid or oleic acid; or an acid anhydridesuch as maleic anhydride, itaconic anhydride or citraconic anhydride.Preferably, one or more carboxylic acids selected from maleic acid,fumaric acid and itaconic acid, or derivatives thereof is used.

[0178] Carboxylic acids other than those described above also can beused simultaneously as needed. Example of such carboxylic acids arealiphatic carboxylic acids having 2 to 24 carbon atoms, such as aceticacid, propionic acid, hexanoic acid, stearic acid, oxalic acid, malonicacid, succinic acid, glutamic acid, adipic acid and sebacic acid;aromatic carboxylic acids having 7 to 18 carbon atoms, such asisophthalic acid and terephthalic acid; and alicyclic carboxylic acidshaving 6 to 20 carbon atoms, such as 1,4-cyclohexanedicarboxylic acidand tetrahydrophthalic acid.

[0179] As the glycol (q), the polyhydric alcohols and polyhydric phenolsamong the active hydrogen-containing compounds previously described forthe polyol (A), and the alkylene oxides having 2 to 8 carbon atomsdescribed above can be used. Preferably, alkylene glycols such asethylene glycol, diethylene glycol, polyethylene glycol, propyleneglycol, polyoxypropylene glycol, 1,3- or 1,4-butanediol, 1,6-hexanedioland neopentyl glycol, and alkylene oxides such as EO, PO, BO and SO areused. More preferably, ethylene glycol, diethylene glycol,1,4-butanediol, 1,6-hexanediol, neopentyl glycol, EO and PO are used.

[0180] The aromatic hydrocarbon monomers (b2-1) include styrene,α-methylstyrene, hydroxylstyrene, chlorostyrene, and the like.

[0181] The unsaturated nitrites (b2-2) include acrylonitrile,methacrylonitrile, and the like.

[0182] The (meth)acrylic acid esters (b2-3) include (meth)acrylic acidalkyl esters (C₁-C₂₄ in the alkyl group) such as methyl(meth)acrylate,butyl(meth)acrylate, nonyl(meth)acrylate, decyl(meth)acrylate,undecyl(meth)acrylate, dodecyl(meth)acrylate, tridecyl(meth)acrylate,tetradecyl(meth)acrylate, pentadecyl(meth)acrylate,hexadecyl(meth)acrylate, octadecyl(meth)acrylate, eicosyl(meth)acrylateand docosyl(meth)acrylate; hydroxypolyoxyalkylene mono(meth)acrylates;and the like.

[0183] Other ethylenically unsaturated compounds (b2-4) include(meth)acrylamide; vinyl-containing carboxylic acids and derivativesthereof, such as (meth)acrylic acid; aliphatic hydrocarbon monomers,such as ethylene and propylene; fluorine-containing vinyl monomers, suchas perfluorooctylethyl methacrylate and perfluorooctylethyl acrylate;nitrogen-containing vinyl monomers, such as diaminoethyl methacrylateand morpholinoethyl methacrylate; vinyl-modified silicone; alkyl olefincompounds, such as α-olefin, β-olefin and polyisobutene; cyclic olefincompounds, such as norbornene, cyclopentadiene and norbornadiene; andthe like.

[0184] Among these, (b2-1) and (b2-2) are preferred, and styrene and/oracrylonitrile are more preferred.

[0185] When using the above method (i) to obtain (I), the amount of (b1)is usually at least 5 mass %, preferably at least 10 mass %,particularly preferably from 15 to 99 mass %, most preferably from 20 to80 mass %, based on the total amount of (b) used.

[0186] By letting the amount of (b1) be at least 5 mass %, an increasein the viscosity of the obtained polymer polyol can be prevented.

[0187] In the production of the polymer polyol compositions of the firstand second inventions, as the ethylenically unsaturated compound (b)used in the methods other than the method (i) of the fifth invention,those having one or more polymerizable vinyl group and usually used inthe production of polymer polyol compositions may be used. For example,(b2-1), (b2-2), (b2-3) and (b2-4) described above or mixtures of two ormore thereof may be used.

[0188] Among these, (b2-1) and (b2-2) are preferred, and styrene and/oracrylonitrile are more preferred.

[0189] In the ethylenically unsaturated compounds used in the methodsother than the method (i), the mass ratios of the aromatic hydrocarbonmonomers (b2-1), the unsaturated nitriles (b2-2), the (meth)acrylic acidesters (b2-3) and other ethylenically unsaturated compounds (b2-4) withrespect to the total amount of (b) used can be changed depending on therequired properties of the polyurethane, etc. Although not particularlylimited, the mass ratios are, for example, as follows.

[0190] (b2-1): usually from 0 to 100 mass %, preferably from 20 to 80mass %.

[0191] (b2-2): usually from 0 to 95 mass %, preferably from 20 to 80mass %.

[0192] (b2-3): usually from 0 to 50 mass %, preferably from 0 to 20 mass%.

[0193] (b2-4): usually from 0 to 10 mass %, preferably from 0 to 5 mass%.

[0194] Furthermore, when the polymer polyol (I) is obtained by themethods other than the method of the fifth invention, by usingpolyfunctional vinyl-containing monomers (b2-5) having two or morefunctional groups (preferably from 2 to 8 functional groups) as at leasta portion of (b) (preferably from 0.05 to 1 mass %), the strength of thepolymer can be increased. The polyfunctional vinyl-containing monomersinclude divinylbenzene, ethylene di(meth)acrylate, polyalkylene (C₂-C₈in the alkylene group) glycol di(meth)acrylate, pentaerythritol triallylether, trimethylolpropane tri(meth)acrylate, and the like.

[0195] In the polymer polyol composition of the eighth invention, theethylenically unsaturated compound (b) contains, as its essentialcomponent, not less than 5 mass % of aterminal-ethylenically-unsaturated-group containing compound (b3) havinga number average molecular weight of 160 to 490 and a solubilityparameter SPb of 9.5 to 13. The number average molecular weight of (b3)is preferably 170 to 480, more preferably 180 to 450, particularlypreferably 182 to 420, most preferably 185 to 400. With a number averagemolecular weight of not less than 160, a polymer polyol composition hasa low viscosity, which is preferable from the viewpoint of handling, andfoams with a good hardness can be obtained as well. In the case where(b3) has a number average molecular weight of not more than 490, apolyurethane foam obtained using this has a good hardness.

[0196] As to the number of ethylenically unsaturated groups in (b3), notless than one ethylenically unsaturated group in average will suffice.The number is preferably 1 to 10, more preferably 1 to 2, particularlypreferably 1. In the case where the number of the ethylenicallyunsaturated groups is less than 1 in average, soluble components inpolyols increase, thereby increasing the viscosity of a polymer polyolobtained, and further, significantly impairing the properties of apolyurethane resin formed using the same. It should be noted that aslong as at least one ethylenically unsaturated group of (b3) (inaverage) is present at a terminal, the other unsaturated groups can bepresent at terminals or at positions that are not terminals.

[0197] More specifically, examples of the foregoing ethylenicallyunsaturated groups include a-alkenyl groups such as (meth)acryloylgroups and allyl groups.

[0198] Furthermore, a molecular weight (X) per one double bond of (b3)is preferably not more than 490, more preferably 160 to 480,particularly preferably 180 to 450, most preferably 185 to 400. In thecase where it is not more than 490, a significant effect of decreasingpolyol-soluble olygomers in a polymer polyol produced by using the samecan be achieved.

[0199] Here, the molecular weight (X) per one double bond of (b3) isdefined as shown by a formula below:

X=1000/N

[0200] where N represents an unsaturation degree of (b3) measured by themethod specified in JIS K-1557.

[0201] Furthermore, (b3) usually has a solubility parameter SPb of 9.5to 13, preferably 9.8 to 12.5, more preferably 10.0 to 12.2. In the casewhere SPb of (b1) is not less than 9.5, a polymer polyol produced usingthe same has a low viscosity. Furthermore, in the case where SPb is notmore than 13, a foam obtained using the polymer polyol has an increasedhardness.

[0202] The solubility parameter herein refers to the parameter expressedby the square root of the ratio of a cohesive energy density to a molarvolume as follows:

[Solubility Parameter](ΔE/V)^(1/2).

[0203] In the above equation, AE indicates a cohesive energy density,and V indicates a molecular volume. The value of V is determined by thecalculation of Robert F. Fedoors et al., which is described, forexample, in Polymer Engineering and Science, Volume 14, pages 147 to154. It is described that the solubility parameters of typical resinsare, for example, as follows: as the values of vinyl-based polymers,polystyrene=10.6, polyacrylonitrile=14.4, poly(methyl methacrylate)=9.9;as the values of polyethers, polyethylene glycol=9.4, polypropyleneglycol=8.7; as the values of polyolefins, polyethylene=8.6,polypropylene=8.0; as the values of polyesters, poly(ethyleneterephthalate)=12.4, poly(butylene terephthalate)=11.7; and as thevalues of polyamides, 6-nylon=11.9, 6,6-nylon=11.9. The values of otherresins also can be calculated by combining the values of respectivechemical bonds shown in the table. For example, the value of polyimideis calculated from the values of pyromellitic acid and1,4-diaminobenzene to be 19.6, and the value of polyurethane iscalculated from 1,4-butanediol and diphenylmethanediisocyanate to be12.3. However, the real values may be more or less different from thesecalculated values, due to a small difference in the structure or thestructures at the terminals of the resins.

[0204] Examples that are preferably used as (b3) include (b31) to (b35)shown below, since with the same, an obtained polymer polyol has a lowviscosity, thereby causing an obtained polyurethane foam to have agreater hardness. Two or more may be used in combination.

[0205] (b31): (poly)oxyalkylene (C₂-C₈ in the alkylene group) ether of aterminal unsaturated alcohol (C₃-C₂₄);

[0206] (b32): compound expressed by a general formula [1] shown below;

[0207] (b33): compound expressed by a general formula [2] shown below;

[0208] (b34): compound expressed by a general formula [3] shown below;

[0209] (b35): compound expressed by a general formula [4] shown below:

CH₂═CRCOO(AO)_(k)COCH₂COCH₃  [1]

CH₂═CRCOO(AO)_(k)[CO(CH₂)_(s)O]_(m)(AO)_(n)H  [2]

CH₂═CRCO[O(CH₂)_(s)CO]_(m)O(AO)_(n)H  [3]

CH₂═CRCOO(AO)_(k)[QO(AO)_(p)]_(r)(O)_(t)H  [4]

[0210]  where:

[0211] R represents a hydrogen atom or a methyl group;

[0212] A represents an alkylene group having 2 to 8 carbon atoms;

[0213] Q represents a residue obtained by removing two OH groups fromdicarboxylic acid;

[0214] k represents an integer of not less than 1 that provides a numberaverage molecular weight of not more than 490;

[0215] n and p represent 0 or integers of not less than 1 that provide anumber average molecular weight of not more than 490;

[0216] s represents an integer of 3 to 7;

[0217] m and r are integers of not less than 1 that provide a numberaverage molecular weight of not more than 490; and

[0218] t represents 0 or 1.

[0219] Here, the number average molecular weight mentioned in the abovedescription, as in the phrase “provides a number average molecularweight of not more than 490”, indicates a number average molecularweight of the foregoing compound.

[0220] Examples of the terminal unsaturated alcohol having 3 to 24carbon atoms in the foregoing (b31) include allyl alcohol, 1-hexen-3-ol,etc. The number of oxyalkylene units in (b31) is usually 1 to 9,preferably 1 to 5, more preferably 1 to 3.

[0221] In the foregoing general formulae [1] to [4], A represents analkylene group having 2 to 8 carbon atoms, an AO unit is usually formedby adding an alkylene oxide having 2 to 8 carbon atoms, and k, n, and pare equivalent to the numbers of added moles of the alkylene oxide,respectively. Furthermore, (poly)oxyalkylene units having 2 to 8 carbonatoms in the alkylene group of (b31) are also usually formed by addingan alkylene oxide having 2 to 8 carbon atoms.

[0222] Examples of the foregoing alkylene oxide include those mentionedin the description about the polyol (A) as alkylene oxides to be addedto an active hydrogen-containing compound. The alkylene oxide ispreferably PO and/or EO.

[0223] k is preferably 1 to 7, more preferably 1 to 5, particularlypreferably 1. n is preferably either 0 or 1 to 7, more preferably either0 or 1 to 5, particularly preferably 0. p is preferably either 0 or 1 to6.

[0224] Examples of Q include a residue obtained by removing two OHgroups from a dicarboxylic acid. Preferable examples of the dicarboxylicacid are those having 4 to 10 carbon atoms. More specifically, theexamples include phthalic acid (including isophthalic acid andterephthalic acid), maleic acid, fumaric acid, and succinic acid.Phthalic acid and succinic acid are preferred.

[0225] The parts of the [CO(CH₂)_(s)O] unit and the [O(CH₂)_(s)CO] unitare usually formed by adding lactone. s is preferably 4 to 6, morepreferably 5. m is preferably 1 to 5, more preferably 1 to 3,particularly preferably 2.

[0226] Furthermore, r is preferably 1 to 5, more preferably 1 or 2,particularly preferably 1.

[0227] Among these (b31) to (b35), (b31) and (b32) are more preferred,and (b31) is particularly preferred.

[0228] As to examples of (b31) to (b35), examples of (b31), forinstance, includes 1 to 5-mole PO and/or EO adducts of allyl alcohol.

[0229] Examples of (b32) include an acetoacetic ester of a compoundobtained by adding 1 to 5 moles of PO and/or EO to 1 mole of(meth)acrylic acid.

[0230] Examples of (b33) include a compound obtained by adding 1 to 5moles of ε-caprolactone to a compound obtained by adding 1 to 5 moles ofPO and/or EO to 1 mole of a (meth)acrylic acid, and a compound obtainedby further adding 1 to 5 moles of PO and/or EO to 1 mole of theforegoing compound.

[0231] Examples of (b34) include a compound obtained by adding 1 to 5moles of ε-caprolactone to 1 mole of a (meth)acrylic acid, and acompound obtained by further adding 1 to 5 moles of PO and/or EO to 1mole of the foregoing compound.

[0232] Examples of (b35) include: a monoester of a compound obtained byadding 1 to 5 moles of PO and/or EO to 1 mole of a (meth)acrylic acidwith the equal number of moles of succinic acid; a monoester of acompound obtained by adding 1 to 5 moles of PO and/or EO to 1 mole of a(meth)acrylic acid with the equal number of moles of maleic acid orfumaric acid; a compound obtained by preparing a monoester of a compoundobtained by adding 1 to 5 moles of PO and/or EO to 1 mole of a(meth)acrylic acid with the equal number of moles of phthalic acid, thenadding 1 to 5 moles of PO and/or EO to 1 mole of the foregoingmonoester; and a monoester of the foregoing compound with the equalnumber of moles of phthalic acid.

[0233] In the polymer polyol composition of the eighth invention, anethylenically unsaturated compound (b2′) having a number averagemolecular weight of less than 500, which is normally used, other than(b3), may be used as the ethylenically unsaturated compound (b).Examples of (b2′) include those mentioned as (b2) and other than (b3).

[0234] As (b), the aforementioned ethylenically unsaturated compounds(b1) having a number average molecular weight of not less than 500 maybe used.

[0235] The content of (b3) in (b) is preferably not less than 2 mass %,more preferably 5 to 80 mass %, particularly preferably 7 to 50 mass %.

[0236] In the case where the content of (b3) is not less than 2 mass %,the obtained polymer polyol has a low viscosity. It is preferred thatthe content of (b3) is not less than 5 mass % [Eighth Invention], but inthe case where the aforementioned reactive dispersant (D1) [including(D11)] is used, the content of the same may be less than 5 mass %. Acomponent other than (b3) in (b) is preferably (b2′).

[0237] In the present invention, the polymerization of (b) can becarried out by, for instance, radical polymerization, coordinatedanionic polymerization, metathesis polymerization, Diels-Alderpolymerization, and the like. Preferably, radical polymerization isemployed.

[0238] Polymerization of the radically polymerizable compound can becarried out in the same way as the polymerization of conventionalpolymer polyols. For example, the method of polymerizing anethylenically unsaturated compound (b) in a polyol (A) containing adispersant (D) in the presence of a polymerization initiator (the methoddescribed in U.S. Pat. No. 3,383,351, etc.) may be employed.

[0239] Furthermore, the polymerization can be carried out either inbatch or continuous systems under atmospheric pressure or increasedpressure, or under reduced pressure. A diluent (C) and a chain transferagent can be used as needed.

[0240] As the radical polymerization initiator, compounds that form afree radical to initiate polymerization may be used. Examples of thecompounds include azo compounds, such as 2,2′-azobisisobutyronitrile,2,2′-azobis(2,4-dimethylvaleronitrile),2,2′-azobis(2-methylbutyronitrile),1,1′-azobis(cyclohexane-1-carbonitrile),2,2′-azobis(2,4,4-trimethylpentane), dimethyl-2,2′-azobis(2-methylpropionate), 2,2′-azobis[2-(hydroxymethyl)propionitrile] and1,1′-azobis(1-acetoxy-1-phenylethane); organic peroxides such asdibenzoyl peroxide, dicumyl peroxide, bis(4-t-butylcyclohexyl)peroxidicarbonate, benzoyl peroxide, lauroyl peroxide and persuccinicacid; and inorganic peroxides, such as persulfate and perborate.Combinations of two or more thereof also may be used.

[0241] The amount of the radical polymerization initiator used isusually from 0.05 to 20 mass %, preferably from 0.1 to 15 mass %,particularly preferably from 0.2 to 10 mass %, based on the amount of(b) used. When the amount of the polymerization initiator used is from0.05 to 20 mass %, the polymerization degree of (b) in the polymerpolyol is sufficiently high, and also the molecular weight is high.Thus, it is excellent in that a polyurethane foam having a sufficientcompressive hardness can be obtained.

[0242] Examples of the diluent (C) used in the radical polymerizationinclude: aromatic hydrocarbon-based solvents such as toluene and xylene;saturated aliphatic hydrocarbon-based solvents having 5 to 15 carbonatoms such as hexane and heptane; unsaturated aliphatichydrocarbon-based solvents having 5 to 30 carbon atoms such as octene,nonene, and decene; ether-based solvents such as dioxane; ester-basedsolvents such as ethyl acetate; nitrile-based solvents such asacetonitrile; and amide-based solvents such as N,N-dimethylformamide andN,N-dimethylacetoamide. Preferred as (C) are aromatic hydrocarbon-basedsolvents since the obtained polymer polyol compositions have lowerviscosities. More preferred is xylene.

[0243] The amount of (C) used is preferably from 0 to 50 mass %, morepreferably from 1 to 40 mass %, based on the amount of (b) used.

[0244] The (C) used is preferably removed therefrom by vacuum strippingafter polymerization, or alternatively (C) may be caused to remain inthe polymer polyol composition or may be added anew, as needed, so thatthe polymer polyol composition has a further reduced viscosity. Examplesof (C) to be contained therein include: the aforementioned unsaturatedaliphatic hydrocarbon-based solvents; aromatic solvents; and fireretardants having a low viscosity (not more than 100 mPa·s/25° C.), forinstance, tris(chloroethyl)phosphate, tris(chloropropyl)phosphate, etc.

[0245] Examples of the chain transfer agent include alkylmercaptans,such as dodecylmercaptan and mercaptoethanol; alcohols, such asisopropyl alcohol, methanol, 2-butanol and allyl alcohol; halogenatedhydrocarbons, such as carbon tetrachloride, carbon tetrabromide andchloroform.

[0246] The amount of the chain transfer agent used is usually from 0 to2 mass %, preferably from 0 to 0.1 mass %, more preferably 0 mass %,based on the amount of (b) used.

[0247] Examples of the polymerization initiator used in thepolymerization methods other than radical polymerization are as follows.In the coordinated anionic polymerization, an initiator composed of anorganic alkyl compound of the metals of I, II and III groups in theperiodic table in combination with a salt of the metals of IV to VIIgroups can be used. Furthermore, in the metathesis polymerization, aninitiator composed of WCl₆ or MoCl₅ in combination with an organicaluminum can be used.

[0248] In the method (ii) [Sixth Invention] to obtain the polymer polyolcomposition (I) comprising separating the polymer particles (B) from apolymer polyol composition obtained by polymerizing (b) in a polyol andmechanically dispersing the polymer particles (B) in (A) not containingsoluble polymers, the polymer particles (B) are vinyl polymer particlesor polymer particles obtained by polycondensation or polyadditionreaction, and usually have a particle size of 0.1 to 50 μm. The finepolymer particles separated from a conventional polymer polyol obtainedby polymerizing an ethylenically unsaturated compound (b) in a polyol inthe presence of a polymerization initiator to form a polymer polyol,adding a solvent to the polymer polyol as needed, and allowing them tosettle by centrifuging are used as the polymer particles (B).Furthermore, fine polymer particles produced by emulsion polymerizationor suspension polymerization, which are known as methods for producingpolymer particles, also can be employed. As the polymer particles (B),it is preferable to use the particles obtained by polymerizing (b) in apolyol (A), because of the easiness of the method steps.

[0249] In the method (ii) [Sixth Invention], examples of the solventused as needed include those mentioned as the diluent (C). As the devicefor mechanically redispersing in the polyol (A) the polymer obtained byadding a solvent to a polymer polyol as needed after polymerization andsubjecting it to centrifugation, any device capable of dispersing orcrushing using the principle of impact, shock or shear can be employedregardless of the mechanism, structure, and material thereof.

[0250] One example of the dispersing or crushing machine used in thepresent invention is a dispersing machine that tears and disperses aliquid by applying pressure and thereby makes it collide against a metalwall (valve) (homogenizer, manufactured by A. P. V. GAURIN, Ltd.).

[0251] The fourth invention of the present invention is a polymer polyolcomposition (III) comprising a polyol (A) and polymer particles (B)dispersed in (A) or a dispersion medium composed of (A) and a diluent(C), the polymer particles (B) being formed by polymerizing anethylenically unsaturated compound (b) in a dispersion medium comprising(A) in the presence of a dispersant (D′) to form polymer particles, andmechanically dispersing or crushing the polymer particles, in which thedifference between the solubility parameter SPd of (D′) and thesolubility parameter SPa of (A) is not more than 0.8. The seventhinvention is a method for producing the polymer polyol composition(III).

[0252] In the fourth invention, the polyol (A) may be used as adispersion medium, either alone or in combination with theaforementioned diluent (C).

[0253] The content of (C) in the dispersion medium may be arbitrary.However, it is usually from 0 to 80 mass %, preferably from 1 to 50 mass%.

[0254] As the dispersant (D′) used in the fourth invention, it isnecessary to choose a dispersant in which the difference between thesolubility parameter SPd of the dispersant and the solubility parameterSPa of the polyol is usually not more than 0.8, preferably not more than0.6, in absolute value. By letting the difference be not more than 0.8in absolute value, the dispersion stability of the polymer polyol isimproved, and aggregation and sedimentation of the polymer particles canbe prevented.

[0255] The solubility parameter herein refers to that described above.

[0256] As one example of the dispersant (D′) of the present invention,the same as those described above for the dispersant (D) may be used, aslong as the condition of the SP value is satisfied.

[0257] As one example of the dispersant (D′), a compound obtained byreacting polypropylene glycol with glycidyl methacrylate has asolubility parameter SPd of 8.8. This is different from the value of SPaby 0.1 when the polyether (A) is polypropylene glycol.

[0258] In the fourth invention, as the ethylenically unsaturatedcompound (b), known compounds having one or more polymerizable vinylgroup and used in the production of polymer polyols can be employed.Specifically, the above described (b2-1), (b2-2), (b2-3) and (b2-4), andmixtures of two or more thereof may be employed.

[0259] Among these, (b2-1) and (b2-2) are preferred, and styrene and/oracrylonitrile are more preferred.

[0260] The mass ratios thereof these with respect to the total amount of(b) can be changed depending on the required properties of thepolyurethane, etc., and are not particularly limited. However, oneexample is as follows.

[0261] (b2-1): usually from 0 to 100 mass %, preferably from 20 to 80mass %

[0262] (b2-2): usually from 0 to 95 mass %, preferably from 20 to 80mass %

[0263] (b2-3): usually from 0 to 50 mass %, preferably from 0 to 20 mass%

[0264] (b2-4): usually from 0 to 10 mass %, preferably from 0 to 5 mass%

[0265] By using the above-mentioned polyfunctional vinyl-containingmonomers (b2-5) having two or more functional groups (preferably from 2to 8 functional groups) at least in a portion of (b) (preferably from0.05 to 1 mass %), the strength of the polymer can be increased.

[0266] The polymer polyol of the fourth invention is characterized inthat it has a low viscosity even when the content of the polymerparticles in the polymer polyol is high. The content of the polymerparticles is usually from 30 to 75 mass %, preferably from 40 to 70 mass%, more preferably from 45 to 60 mass %. When the content of the polymerparticles is at least 30 mass %, a polyurethane foam having a sufficientcompressive hardness can be obtained, and this is preferred.Furthermore, by letting the content of the polymer particles be not morethan 75 mass %, aggregation and sedimentation of the polymer particlescan be prevented, and the polymer polyol can exhibit good handlingproperties.

[0267] In the fourth invention, the polymerization of the polymer polyolcan be carried out in the presence of a dispersant (D′) in the samemanner as the above polymerization method described for a conventionalpolymer polyol.

[0268] In the fourth invention, as the polymerization initiator used inthe polymerization of the polymer polyol, the radical polymerizationinitiator described above for the first and second inventions, etc. canbe employed.

[0269] The amount of the radical polymerization initiator used isusually from 0.05 to 10 mass %, preferably from 0.1 to 5 mass %, morepreferably from 0.2 to 2.5 mass %, based on the mass of theethylenically unsaturated compound (b). By letting the amount of thepolymerization initiator used be at least 0.05 mass %, a decrease in thepolymerization degree of (b) can be prevented, and the content of thepolymer particles formed from (b) in the polymer polyol can besufficiently high. Furthermore, by letting the amount of thepolymerization initiator used be not more than 10 mass %, a decrease inthe molecular weight of the polymer particles can be prevented, and apolyurethane foam having a sufficient compressive hardness can beobtained.

[0270] Furthermore, if necessary, the polymerization can be carried outin the presence of the aforementioned chain transfer agent.

[0271] In the fourth invention, the polymer polyol (III) can be obtainedby physically and mechanically dispersing or crushing the polymerparticles dispersed in the polymer polyol obtained by polymerization. Inthis case, the polymer particles (B) are not separated temporally from apolymer polyol. But the polymer particles (B) are retained in a polymerpolyol, and are dispersed further mechanically. For example, the polymerpolyol may be dispersed further by (i) forwarding it from apolymerization reaction vessel to a dispersing or crushing machine; orby (ii) forwarding it from a polymerization vessel to a reservoir andstoring it temporarily, and then forwarding it to a dispersing orcrushing machine. The mechanism of the dispersing or crushing is, forexample, to utilize impact or shock, or shear. With the ability ofdispersing or crushing by utilizing these principles, any device can beused regardless of its mechanism, structure and material. One example ofthe dispersing or crushing machine used in the present invention is adispersing machine that tears and disperses a liquid by applyingpressure to the liquid and make it collide against a valve (homogenizer;manufactured by A. P. V. GAURIN, Ltd.).

[0272] The polymer particles (B) in the polymer polyol afterpolymerization usually have a particle size of not more than 3 μm,preferably not more than 2 μm. The polymer polyol containing thesepolymer particles is put in a dispersing or crushing machine, anddispersed or crushed forcefully, so that the size of the polymerparticles (B) is reduced. Thus, the polymer polyol (III) is obtained.The particle size of the polymer particles after dispersing or crushingis usually not more than 1 μm, preferably not more than 0.5 μm. [Theparticle size is measured by a light scattering particle sizedistribution meter LA-700 (manufactured by HORIBA, Ltd.).]

[0273] The temperature after dispersing or crushing is in the range of0° C. to 100° C., preferably 5° C. to 50° C. Furthermore, when thepolymer particles (B) in the polymer polyol are mechanically dispersedor crushed, the polymer polyol may be diluted with a solvent, ifnecessary. As the solvent, those exemplified above for (C) can beemployed. The mechanical dispersing or crushing of the polymer polyol isusually carried out from 1 to 20 times, preferably from 2 to 10 times.The solvent is removed under reduced pressure after dispersing.

[0274] The removal of the solvent is carried out under atmosphericpressure or reduced pressure (e.g. reduction degree of 20 to 30 mmHg) ata temperature of 60 to 100° C. It is preferable that the remainder ofthe solvent is not more than 50 ppm with respect to the polymer polyol.

[0275] In the fourth invention, the content of the polymer particles inthe polymer polyol is usually from 30 to 75 mass %, and the viscosity ofthe polymer polyol obtained by polymerization is from 2,000 to 100,000mPa·s (25° C.). Furthermore, the viscosity resulting from the physicaland mechanical dispersing or crushing after polymerization is from 500to 20,000 mPa·s (25° C.).

[0276] In the fourth invention, the viscosity of the polymer polyol(III) may be changed depending on the content of the polymer particles.However, it is usually from 500 to 20,000 mPa·s (25° C.), preferablyfrom 700 to 15,000 mPa·s (25° C.). By letting the viscosity of thepolymer polyol (III) be not more than 20,000 mPa·s (25° C.), the polymerpolyol can exhibit good handling properties. Furthermore, by letting theviscosity of the polymer polyol (III) be at least 500 mPa·s (25° C.), apolyurethane foam having a more sufficient compressive hardness can beobtained.

[0277] Among the methods of the fifth, sixth, and seventh inventions,the methods of the fifth and sixth inventions are preferred, and themethod of the fifth invention is more preferred. However, as describedabove, as methods for obtaining the polymer polyol compositions of thefirst and second inventions, the methods (iii) to (v) are particularlypreferred, and the method (iii) in combination with the method (iv) or(v) is most preferred.

[0278] The eleventh invention of the present invention is a method forproducing a polyurethane resin using any of the polymer polyolcompositions of the first to fourth and eighth to tenth inventions atleast in a portion of a polyol component.

[0279] In the method for producing a polyurethane resin by reacting apolyol component with a polyisocyanate component in the presence of acatalyst, a blowing agent, a foam stabilizer and other additives asneeded, the polymer polyol compositions of the present invention can beused in combination with known other active hydrogen atom-containingcompounds, if necessary, as a polyol component. As the other activehydrogen atom-containing compound, other types of high molecular polyolsor monools (T) and low molecular active hydrogen atom-containingcompounds (U) normally used in the production of polyurethane can beused.

[0280] As the other types of high molecular polyols or monools (T),polyether polyols, polyester polyols, the other various types of polyolsand monools, and modified polyols; and mixtures thereof can be used.

[0281] The polyether polyols include those exemplified above for thepolyol (A1).

[0282] The polyester polyols include polyester polyols mentioned aboveas examples of (A2), and the like.

[0283] Examples of the other various types of polyols or monoolsinclude: diene-type polyols such as polybutadiene polyol, andhydrogen-added products of the same; hydroxyl group-containing vinylpolymers such as acryl-base polyols; polyols based on natural oils suchas castor oil; modification products of natural oil-based polyols;terminal radical-polymerizable-functional group-containing activehydrogen compound disclosed in EP 1 006 133; high-molecular polyolsother than those specifically mentioned in the present specification.

[0284] These other types of high-molecular polyols or monools (T)preferably have from 2 to 8 hydroxyl groups, further preferably from 3to 8 hydroxyl groups; and usually have a hydroxyl equivalent of not lessthan 200, preferably 300 to 4000, more preferably 400 to 3000.

[0285] The polyether polyols are particularly preferred.

[0286] As the low molecular active hydrogen atom-containing compounds(U), compounds having at least two (preferably from 2 to 3, morepreferably 2) active hydrogen atoms (hydroxyl group, amino group,mercapto group, etc., preferably hydroxyl group) and having anequivalent of less than 200 (preferably from 30 to 180) per one activehydrogen atom. The compound (U) preferably has a molecular weight of notmore than 500, more preferably from 60 to 400. Examples of the compound(U) include low molecular polyols and amino alcohols.

[0287] The low molecular polyols include dihydric alcohols, such asethylene glycol, diethylene glycol, propylene glycol, dipropyleneglycol, 1,4-butanediol, neopentyl glycol and hexane diol; polyhydricalcohols having three or more hydroxyl groups, such as glycerol,trimethylolpropane, pentaerythritol, diglycerol, a-methylglucoside,sorbitol, xylytol, mannitol, dipentaerythritol, glucose, fructose andsucrose; alkylene oxide adducts of polyhydric alcohols, having a lowmolecular weight (e.g. molecular weight of 200 to 400), e.g.polyethylene glycol and polypropylene glycol; and low molecular diolshaving a ring structure, e.g. PO adducts of bisphenol A. The aminoalcohols include mono- or dialkanol amines (e.g. monoethanol amine,diethanol amine, monopropanol amine, etc.).

[0288] Among these preferred are the low molecular polyols, particularlydiols. Specific examples are ethylene glycol, 1,4-butanediol, neopentylglycol, 1,6-hexanediol, and mixtures of two or more thereof.

[0289] In the method for producing a polyurethane according to theeleventh invention, the amount of the polymer polyol composition of thepresent invention in the polyol component (Z) [the polymer polyolcomposition, and as needed (T) and/or (U)] is preferably at least 5 mass%, more preferably at least 10 mass %, particularly preferably at least20 mass %. When the amount of the polymer polyol composition is at least5 mass %, a desired compressive hardness of a polyurethane foam can beobtained easily. The content of (B) in the polyol component (Z) ispreferably from 5 to 75 mass %, more preferably from 7 to 55 mass %. Inthe case where the amount is in the foregoing range, excellent foamhardness and excellent flowability of the foam forming material mixturecan be obtained.

[0290] Furthermore, it is preferable that the content of (T) is from 0to 95 mass %, more preferably from 0 to 80 mass %. When the content of(T) is not more than 95 mass %, a desired compressive strength of apolyurethane foam can be obtained easily.

[0291] Furthermore, it is preferable that the content of (U) is from 0to 30 mass %, more preferably from 0 to 10 mass %. When the content of(U) is not more than 30 mass %, the temperature of the developed heat atthe time of reaction does not become too high, so that the risk ofscorching is eliminated.

[0292] As the polyisocyanate component used when producing apolyurethane resin of the eleventh invention, known organicpolyisocyanates traditionally used for producing polyurethane resins canbe employed.

[0293] Such polyisocyanates include those mentioned above as examples ofthe polyisocyanate (f).

[0294] Among these preferred are 2,4- and 2,6-TDI, mixtures of isomersthereof, and crude TDI; 4,4′- and 2,4′-MDI, mixtures of isomers thereof,and crude MDI; and modified polyisocyanates derived from thesepolyisocyates and containing a urethane group, carbodiimide group,allophanate group, urea group, biuret group or isocyanurate group.

[0295] The isocyanate index [equivalent ratio of (NCO groups/activehydrogen atom-containing groups)×100] when producing a polyurethaneresin is usually from 80 to 140, preferably from 85 to 120, morepreferably from 95 to 115. Furthermore, the isocyanate index also can beconsiderably higher than the above range (e.g. from 300 to 1000) toincorporate a polyisocyanate group in the polyurethane.

[0296] When producing a polyurethane resin, a catalyst normally used ina polyurethane-forming reaction may be used to accelerate the reaction.For example, amine-based catalysts (e.g. tertiary amines such astriethylenediamine and N-ethylmorpholine;1,8-diaza-bicyclo[5.4.0]undecene-7 (“DBU” produced by San-Apro Ltd.),etc.), tin-based catalysts (e.g. stannous octoate, dibutyl tindilaurate, etc.), other metal catalysts (e.g. lead octoate), andisocyanurating catalysts disclosed in U.S. Pat. No. 4,299,924 may beemployed. Among these, preferred are amine-based catalysts and/ortin-based catalysts. The amount of the catalyst is preferably from 0.001to 5 mass %, based on the mass of the reaction mixture.

[0297] In the method of the eleventh invention, the polyurethanereaction may be carried out in the presence of a normally used blowingagent as needed, so that a polyurethane foam (preferably having afoaming rate of 5 to 100) is obtained.

[0298] As the blowing agent, at least one selected from hydrogenatom-containing halogenated hydrocarbons, water, low boiling pointhydrocarbons, liquefied carbon dioxide, and the like may be used.

[0299] Specific examples of the hydrogen atom-containing halogenatedhydrocarbons are those of HCFC (hydrochlorofluorocarbon) type (e.g.HCFC-123, HCFC-141b, HCFC-22 and HCFC-142b); those of HFC(hydrofluorocarbon) type (e.g. HFC-134a, HFC-152a, HFC-356mff,HFC-236ea, HFC-245ca, HFC-245fa and HFC-365mfc); and the like.

[0300] Among these, preferred are HCFC-141b, HFC-134a, HFC-356mff,HFC-236ea, HFC-245ca, HFC-245fa and HFC-365mfc, and combinations of twoor more thereof.

[0301] The low boiling point hydrocarbons usually have a boiling pointof −5 to 70° C. Specific examples thereof include butane, pentane,cyclopentane, and mixtures thereof.

[0302] When a hydrogen atom-containing halogenated hydrocarbon compoundis used, the amount used is usually not more than 50 mass parts,preferably from 5 to 45 mass parts, with respect to 100 mass parts ofthe total polyol component (Z).

[0303] When a low boiling point hydrocarbon is used, the amount used isusually not more than 45 mass parts, preferably from 5 to 40 mass parts,with respect to 100 mass parts of (Z).

[0304] When liquefied carbon dioxide is used, the amount used is usuallynot more than 30 mass parts, preferably from 5 to 25 mass parts, withrespect to 100 mass parts of (Z).

[0305] When a combination of a hydrogen atom-containing halogenatedhydrocarbon and water is used, the amount of the hydrogenatom-containing halogenated hydrocarbon used is usually not more than 45mass parts, preferably from 5 to 40 mass parts, with respect to 100 massparts of (Z), and the amount of water used is usually not more than 10mass parts, preferably from 0.5 to 8 mass parts, with respect to 100mass parts of (Z).

[0306] When a combination of a low boiling point hydrocarbon and wateris used, the amount of the low boiling point hydrocarbon used is usuallynot more than 40 mass parts, preferably from 2 to 35 mass parts, withrespect to 100 mass parts of (Z), and the amount of water used isusually not more than 10 mass parts, preferably from 0.5 to 8 massparts, with respect to 100 mass parts of (Z).

[0307] When a combination of liquefied carbon dioxide and water is used,the amount of the liquefied carbon dioxide used is usually not more than25 mass parts, preferably from 0.1 to 20 mass parts, with respect to 100mass parts of (Z), and the amount of water used is usually not more than10 mass parts, preferably from 0.5 to 8 mass parts, with respect to 100mass parts of (Z).

[0308] When water alone is used as the blowing agent, the amount ofwater used is usually from 0.1 to 30 mass parts, preferably from 1 to 20mass parts, with respect to 100 mass parts of (Z).

[0309] In the method of the eleventh invention, if necessary, thereaction may be carried out in the presence of a foam stabilizer orother additive, such as those described below.

[0310] For example, the reaction can be carried out in the presence of aknown additive, such as a foam stabilizer (based on dimethyl siloxane,polyether modified dimethyl siloxane, etc.), a coloring agent (dyes,pigments, carbon black, etc.), a plasticizer (phthalic acid esters,adipic acid esters, etc.), an organic filler (synthetic staple fibers,hollow microsphere composed of a thermoplastic or thermosetting resin,etc.), an inorganic filler [inorganic salts (calcium carbonate, bariumsulfate, etc.), inorganic fibers (glass fibers, carbon fibers, etc.),whiskers (potassium titanate whisker, etc.)], a flame retardant(phosphoric acid esters, halogenated phosphoric acid esters, melamines,phosphazene derivatives, etc.), an age retardant (based on triazole,benzophenone, etc.), an antioxidant (based on hindered phenol, hinderedamine, etc.), an adhesive (modified polycaprolactone polyol, etc.), aninternal mold release agent, an antibacterial agent, or the like.

[0311] The amounts of these additives used with respect to 100 massparts of the polyol component (Z) are as follows. The amount of the foamstabilizer used is preferably not more than 10 mass parts, morepreferably from 0.2 to 5 mass parts. The amount of the coloring agentused is preferably not more than 1 mass parts. The amount of theplasticizer used is preferably not more than 10 mass parts, morepreferably not more than 5 mass parts. The amount of the organic fillerused is preferably not more than 50 mass parts, more preferably not morethan 30 mass parts. The amount of the inorganic filler used ispreferably not more than 50 mass parts, more preferably not more than 30mass parts. The amount of the flame retardant used is preferably notmore than 20 mass parts, more preferably from 5 to 15 mass parts. Theamount of the age retardant used is preferably not more than 1 massparts, more preferably from 0.01 to 0.5 mass parts. The amount of theantioxidant used is preferably not more than 1 mass parts, morepreferably from 0.01 to 0.5 mass parts. Among the aforementionedadditives, the amount of the additives other than these is preferablynot more than 1 mass part.

[0312] Production of a polyurethane resin can be carried out byconventional methods, for example, one shot method, semiprepolymermethod, prepolymer method, and the like.

[0313] In the production of a polyurethane resin, normally usedproduction devices can be employed. When no solvent is used, forexample, a device such as a kneader or extruder can be employed. Forexample, various types of non-foamed or foamed polyurethane resins canbe produced within a closed or open mold. A packing rate [(density onmold foaming/density on free foaming)×100] in the case where a foamedpolyurethane resin is produced using a closed mold is preferably 110 to200% In the production of a polyurethane resin, usually the materialsare mixed and reacted using a mechanical device at a low pressure orhigh pressure. Furthermore, in the production of a polyurethane resin,the air dissolved in the materials or a gas such as air intermixed atthe time of mixing can be removed by a vacuum method before or aftermixing the raw materials (particularly before mixing the raw materials).

[0314] The polymer polyols obtained by the methods of the presentinvention are useful for producing polyurethane foam, particularlyflexible molded foams and slabstock foams. Furthermore, the polymerpolyols also can be used for molding by the RIM (reaction injectionmolding) method. The polyurethane resin produced using the polymerpolyol composition of the present invention is employed as, forinstance, polyurethane foams used in interiors of cars, and interiorfittings such as furniture. Furthermore, they are used as materials forsealants, synthetic leather, etc.

EXAMPLES

[0315] The present invention is described further in detail withreference to the following examples. However, the present invention isnot limited to these examples in any way. In the following, the valuesof parts, percentage, and ratio indicate those of mass parts, masspercentage, and mass ratio, respectively.

[0316] The compositions, symbols, etc. of the materials used in theexamples and comparative examples are as follows:

[0317] (1) Polyol (A)

[0318] G50: a polyol obtained by adding on average 50 moles of PO toglycerol, and having a number-average molecular weight (hereinafter alsoreferred to as Mn) of 3,000, a hydroxyl value of 56, and a viscosity of500 mPa·s (25° C.).

[0319] (2) Reactive Unsaturated Group-Containing Carboxylic Acid (p)

[0320] MA: maleic anhydride

[0321] IA: itaconic anhydride

[0322] (3) Saturated Carboxylic Acid

[0323] AA: adipic acid

[0324] FA: phthalic acid

[0325] (4) Glycol (q)

[0326] EG: ethylene glycol

[0327] DEG: diethylene glycol

[0328] PP-200: polyoxypropylene glycol (number-average molecular weightof 200)

[0329] PP-400: polyoxypropylene glycol (number-average molecular weightof 400)

[0330] PO: propylene oxide

[0331] (5) Other Ethylenically Unsaturated Compound (b2)

[0332] AN: acrylonitrile

[0333] St: styrene

[0334] (6) Dispersant (D)

[0335] GMAP: equimolar glycidyl methacrylate adducts of polypropyleneglycol (number-average molecular weight of 3,000)

[0336] SAN: acrylonitrile/styrene=80/20 mass % copolymer (number-averagemolecular weight of 5,000)

[0337] Reactive dispersant (D1-1): dispersant produced in Preparation

Example 11

[0338] Reactive dispersant (D1-2): dispersant produced in Preparation

Example 12

[0339] Reactive dispersant (D1-3): dispersant produced in Preparation

Example 13

[0340] (7) Polymerization Initiator

[0341] AVN: 2,2′-azobis(2,4-dimethylvaleronitrile)

[0342] (8) Organic Polyisocyanate

[0343] TDI-80: “CORONATE T-80” [manufactured by NIPPON POLYURETHANEINDUSTRY CO., LTD.]

[0344] (9) Catalyst

[0345] Catalyst A: “Neostann U-28” (stannous octoate) [manufactured byNITTO KASEI CO., LTD.]

[0346] Catalyst B: “DABCO” (triethylenediamine) [manufactured by NIPPONNYUKAZAI CO, LTD.]

[0347] Catalyst C: “DABCO33LV” (33 mass % dipropylene glycol solution ofDABCO) [manufactured by SANKYO AIR PRODUCTS CO., LTD.]

[0348] TBT: tetrabutyl titanate [manufactured by NACALAI TESQUE, INC.]

[0349] (10) Foam Stabilizer

[0350] “F-242T”: polyether siloxane polymer [manufactured by Shin-EtsuSilicone Co., Ltd.]

[0351] Compositions etc. of materials used in Preparation Examples 11 to13, expressed by abbreviations, are as follows.

[0352] (11) Unsaturated Monofunctional Active Hydrogen Compound (e)

[0353] HEMA:2-hydroxy ethyl methacrylate;

[0354] HEA: 2-hydroxy ethyl acrylate,

[0355] (12) Reactive Dispersant-Producing Catalyst

[0356] TBT: tetrabutyl titanate [manufactured by NACALAI TESQUE, INC.]

[0357] (13) Reactive Dispersant Producing Polyisocyanate (f)

[0358] TDI: “CORONATE T-80” [manufactured by NIPPON POLYURETHANEINDUSTRY CO., LTD.]

[0359] (14) Polyol (a)

[0360] Polyol (a-1): polyol obtained by adding 104 moles in average ofPO to pentaerythritol and subsequently adding 19 moles in average of EO,the polyol having a content of EO of 12% and a hydroxyl value of 32.

[0361] Furthermore, the number-average molecular weight, unsaturationdegree, viscosity, polyol-soluble polymer, and dispersion stability weremeasured as follows.

[0362] [Number-Average Molecular Weight]

[0363] Machine type: HLC-8120GPC (liquid chromatograph manufactured byTOSOH CORPORATION) Columns:  TSK gel Super H4000 +TSK gel Super H3000+TSK gel Super H2000 (all are manufactured by TOSOH CORPORATION)

[0364] Column temperature: 40° C. Detector: RI (Refractive Index)Solvent: tetrahydrofuran Flow rate: 0.6 ml/min Concentration of sample:0.25 mass % Injected amount: 10 μl Standard: polystyrene (manufacturedby TOSOH CORPORATION; TSK STANDARD POLYSTYRENE)

[0365] CORPORATION; TSK STANDARD POLYSTYRENE)

[0366] [Unsaturation Degree]

[0367] Unsaturation degree was measured in accordance with the methodspecified in JIS K-1557.

[0368] [Viscosity]

[0369] Machine type: BL-type viscosimeter (manufactured by TOKIMEC INC.)

[0370] Measurement temperature: 25° C.

[0371] Rotor No.: No. 3 or No. 4

[0372] Rotation count: According to the rotation count described abovewith respect to the measurement of viscosity in the description of theinequality (1) concerning the viscosity of V(mPa·s).

[0373] [Polyol-Soluble Polymer]

[0374] Polyol-soluble polymer was measured according to the abovedescribed method. However, in preparative liquid chromatography, thefollowing conditions were used.

[0375] Machine type: LC-09 (manufactured by NIHON BUNSEKIKOGYO CO.,LTD.) Columns:  JAIGEL-1H +JAIGEL- 2H +JAIGEL- 3H (All are manufacturedby NIHON BUNSEKIKOGYO CO., LTD.)

[0376] (All are manufactured by NIHON BUNSEKIKOGYO CO., LTD.) Columntemperature: 40° C. Detector: RI Solvent: chloroform Flow rate: 2.5ml/min Concentration of sample: 0.25 mass Injected amount: 4 ml × 12times

[0377] [Dispersion Stability —1]

[0378] (i) A polymer polyol composition was put into a sealed 140ml-volume container made of glass (sample bottle), and allowed to standin a thermostat at 50° C. for 30 days.

[0379] (ii) Thereafter, dispersion stability was estimated visually.

[0380] Standard of Evaluation

[0381] ∘: There was no sediment, and dispersion was uniform.

[0382] Δ: There was a sediment, but it was redispersed uniformly aftertipping the sample bottle down five times.

[0383] X: There was a sediment, and it was not redispersed after tippingthe sample bottle down five times.

[0384] [Dispersion Stability —2]

[0385] (i) A polymer polyol composition was put into a sealed 140ml-volume container made of glass (sample bottle), and allowed to standin a thermostat at 70° C. for 30 days.

[0386] (ii) Thereafter, dispersion stability was estimated visually.

[0387] Standard of Evaluation

[0388] ∘: There was no sediment, and dispersion was uniform.

[0389] Δ: There was a sediment, but it was redispersed uniformly aftertipping the sample bottle down five times.

[0390] X: There was a sediment, and it was not redispersed after tippingthe sample bottle down five times.

Preparation Example 1 Preparation of a Radically PolymerizableCompound—1

[0391] Into a four-neck flask of 1-liter volume equipped with a Dimrothcondenser and a Dean-Stark trap, 98 parts of MA and 440 parts of PP-400were put. After substituting nitrogen for the air in the flask, thetemperature of the mixture was increased to 80° C. while stirring themixture in the nitrogen atmosphere (until the reaction was completed),and the temperature was maintained for 1 hour. Then, the temperature ofthe mixture was increased to 170° C., and allowed to react at the sametemperature for 6 hours. Then, 0.02 parts of TBT was put into the flask,and allowed to react at 170° C. for 2 hours. Thus, an unsaturatedpolyester (b1(i)) having a number-average molecular weight of 5400, ahydroxyl value of 21 mgKOH/g and an unsaturation degree of 1.86 (X=538)was obtained. In the above, X is the molecular weight per one doublebond as defined previously.

Preparation Example 2 Preparation of a Radically PolymerizableCompound—2

[0392] Using the same apparatus and method as in Preparation Example 1,and using 294 parts of MA and 800 parts of PEG-200, an unsaturatedpolyester (b1(ii)) having a number-average molecular weight of 1094, ahydroxyl value of 103 mgKOH/g and an unsaturation degree of 2.74 (X=365)was obtained.

Preparation Example 3 Preparation of a Radically PolymerizableCompound—3

[0393] Using the same apparatus and method as in Preparation Example 1,and using 98 parts of MA and 240 parts of PP-200, an unsaturatedpolyester (b1(iii)) having a number-average molecular weight of 3400, ahydroxyl value of 33 mgKOH/g and an unsaturation degree of 2.96 (X=338)was obtained.

Preparation Example 4 Preparation of a Radically PolymerizableCompound—4

[0394] Using the same apparatus and method as in Preparation Example 1,and using 118 parts of IA and 440 parts of PP-400, an unsaturatedpolyester (b1(iv)) having a number-average molecular weight of 5600, ahydroxyl value of 20 mgKOH/g, and an unsaturation degree of 1.79 (X=559)was obtained.

Preparation Example 5 Preparation of a Radically PolymerizableCompound—5

[0395] Into a pressure reaction device of 1.5-liter volume, 98 parts ofMA, 400 parts of PP-400, 296 parts of FA, and 0.11 part ofN-ethylmorpholine were put. After substituting nitrogen for the air inthe flask, the temperature of the mixture was increased to 120° C. whilestirring it in the nitrogen atmosphere (until the reaction wascompleted), and the temperature was maintained for 2 hours. Then, 232parts of PO was blown into the reaction mixture at 120° C. and at apressure of 0.3 mPa·s over 6 hours. Then, it was allowed to react at120° C. for another two hours. Thus, an unsaturated polyester (b1(v))having a number-average molecular weight of 1100, a hydroxyl value of102 mgKOH/g and an unsaturation degree of 0.98 (X=1020) was obtained.

Preparation Example 6 Preparation of a Radically PolymerizableCompound—6

[0396] Using the same apparatus and method as in Preparation Example 1,and using 280 parts of MA and 370 parts of DEG, an unsaturated polyester(b1(vi)) having a number-average molecular weight of 1000, a hydroxylvalue of 112 mgKOH/g and an unsaturation degree of 4.34 (X=230) wasobtained.

Preparation Example 7 Preparation of a Radically PolymerizableCompound—7

[0397] Using the same apparatus and method as in Preparation Example 1,and using 390 parts of MA and 284 parts of EG, an unsaturated polyester(b1(vii)) having a number-average molecular weight of 920, a hydroxylvalue of 122 mgKOH/g and an unsaturation degree of 5.49 (X=182) wasobtained.

Example 1 Production of a Polymer Polyol Composition (Hereinafter alsoReferred to as Polymer Polyol)—1

[0398] Into a four-neck flask of 1-liter volume equipped with a Dimrothcondenser, 10 parts of SAN and 440 parts of G50 were put. Aftersubstituting nitrogen for the air in the flask, while stirring themixture in the nitrogen atmosphere (until the polymerization wascompleted), the temperature of the mixture was increased to 130° C.Then, a material previously prepared by mixing 250 parts of theunsaturated polyester (b1(i)), 150 parts of AN and 100 parts of St, anda material previously prepared by mixing 50 parts of G50 and 1 part ofAVN were dropped continuously over 1 hour, each using a dropping pump,at the same time. The reaction mixture was polymerized at 130° C. for 2hours, and a polymer polyol (F-1) having a content of polymer particlesof 50%, a hydroxyl value of 28 mgKOH/g and a viscosity of 4500 mPa·s(25° C.) was obtained.

Example 2 Production of a Polymer Polyol—2

[0399] Into a four-neck flask of 1-liter volume equipped with a Dimrothcondenser, 10 parts of SAN and 390 parts of G50 were put. Aftersubstituting nitrogen for the air in the flask, while stirring themixture in the nitrogen atmosphere (until the polymerization wascompleted), the temperature of the mixture was increased to 130° C.Then, a material previously prepared by mixing 200 parts of theunsaturated polyester (b1(ii)), 150 parts of AN and 200 parts of St, anda material previously prepared by mixing 50 parts of G50 and 1 part ofAVN were dropped continuously over 1 hour, each using a dropping pump,at the same time. The reaction mixture was polymerized at 130° C. for 2hours, and a polymer polyol (F-2) having a content of polymer particlesof 55%, a hydroxyl value of 25 mgKOH/g and a viscosity of 4800 mPa·s(25° C.) was obtained.

Example 3 Production of a Polymer Polyol—3

[0400] Into a four-neck flask of 1-liter volume equipped with a Dimrothcondenser, 10 parts of SAN and 490 parts of G50 were put. Aftersubstituting nitrogen for the air in the flask, while stirring themixture in the nitrogen atmosphere (until the polymerization wascompleted), the temperature of the mixture was increased to 130° C.Then, a material previously prepared by mixing 50 parts of theunsaturated polyester (b1(iii)), 200 parts of AN and 200 parts of St,and a material previously prepared by mixing 50 parts of G50 and 1 partof AVN were dropped continuously over 1 hour, each using a droppingpump, at the same time. The reaction mixture was polymerized at 130° C.for 2 hours, and a polymer polyol (F-3) having a content of polymerparticles of 45%, a hydroxyl value of 31 mgKOH/g and a viscosity of 4000mPa·s (25° C.) was obtained.

Example 4 Production of Polymer Polyol—4

[0401] Into a four-neck flask of 1-liter volume equipped with a Dimrothcondenser, 10 parts of SAN and 340 parts of G50 were put. Aftersubstituting nitrogen for the air in the flask, while stirring themixture in the nitrogen atmosphere (until the polymerization wascompleted), the temperature of the mixture was increased to 130° C.Then, a material previously prepared by mixing 400 parts of theunsaturated polyester (b1(iv)), 100 parts of AN and 100 parts of St, anda material previously prepared by mixing 50 parts of G50 and 1 part ofAVN were dropped continuously over 1 hour, each using a dropping pump,at the same time. The reaction mixture was polymerized at 130° C. for 2hours, and a polymer polyol (F-4) having a content of polymer particlesof 60%, a hydroxyl value of 22 mgKOH/g and a viscosity of 6200 mPa·s(25° C.) was obtained.

Example 5 Production of a Polymer Polyol—5

[0402] Into a four-neck flask of 1-liter volume equipped with a Dimrothcondenser, 10 parts of SAN and 440 parts of G50 were put. Aftersubstituting nitrogen for the air in the flask, while stirring themixture in the nitrogen atmosphere (until the polymerization wascompleted), the temperature of the mixture was increased to 130° C.Then, a material previously prepared by mixing 250 parts of theunsaturated polyester (b1(iv)), 150 parts of AN and 100 parts of St, anda material previously prepared by mixing 50 parts of G50 and 1 part ofAVN were dropped continuously over 1 hour, each using a dropping pump,at the same time. The mixture was polymerized at 130° C. for 2 hours,and a polymer polyol (F-5) having a content of polymer particles of 50%,a hydroxyl value of 28 mgKOH/g, and a viscosity of 4700 mPa·s (25° C.)was obtained.

Example 6 Production of a Polymer Polyol—6

[0403] Into a four-neck flask of 1-liter volume equipped with a Dimrothcondenser, 10 parts of SAN and 440 parts of G50 were put. Aftersubstituting nitrogen for the air in the flask, while stirring themixture in the nitrogen atmosphere (until the polymerization wascompleted), the temperature of the mixture was increased to 130° C.Then, a material previously prepared by mixing 250 parts of theunsaturated polyester (b1(v)), 150 parts of AN and 100 parts of St, anda material previously prepared by mixing 50 parts of G50 and 1 part ofAVN were dropped continuously over 1 hour, each using a dropping pump,at the same time. The mixture was polymerized at 130° C. for 2 hours,and a polymer polyol (F-6) having a content of polymer particles of 50%,a hydroxyl value of 28 mgKOH/g and a viscosity of 4900 mPa·s (25° C.)was obtained.

Example 7 Production of a Polymer Polyol—7

[0404] Into a four-neck flask of 1-liter volume equipped with a Dimrothcondenser, 500 parts of the unsaturated polyester (b1(vi)) was put.After substituting nitrogen for the air in the flask, while stirring themixture in the nitrogen atmosphere (until the polymerization wascompleted), the temperature of the mixture was increased to 130° C.Then, a material previously prepared by mixing 50 parts of SAN and 400parts of G50 was put, and stirred at 130° C. for 3 hours. Then, amaterial previously prepared by mixing 50 parts of G50 and 1 part of AVNwas dropped continuously over 1 hour using a dropping pump. The mixturewas polymerized at 130° C. for 2 hours, and a polymer polyol (F-7)having a content of polymer particles of 50%, a hydroxyl value of 28mgKOH/g and a viscosity of 5500 mPa·s (25° C.) was obtained.

Example 8 Production of a Polymer Polyol—8

[0405] Using the same apparatus and method as in Example 7, and usingthe unsaturated polyester (b1(vii)) in place of the unsaturatedpolyester (b1(vi)), a polymer polyol (F-8) having a content of polymerparticles of 50%, a hydroxyl value of 28 mgKOH/g and a viscosity 5640mPa·s (25° C.) was obtained.

Example 9 Production of a Polymer Polyol—9

[0406] Into a four-neck flask of 2-liter volume equipped with athermoregulator, a vacuum mixing blade, a dropping pump, a pressurereducing device, a Dimroth condenser, and an inlet and an outlet fornitrogen, 50 parts of G50 was put, and heated at 125° C. while stirring.Then, a material previously prepared by mixing 450 parts of St, 300parts of AN, 20 parts of GMAP, 680 parts of G50 and 4 parts of AVN wasdropped continuously over 4 hours using a dropping pump, andpolymerization was carried out. Furthermore, unreacted monomers wereremoved by stripping under reduced pressure.

[0407] Thus, a comparative polymer polyol (F-9) having a content ofpolymer particles of 50%, a hydroxyl value of 28, and a viscosity of20,000 mPa·s (25° C.) was obtained.

[0408] To 800 parts of the polymer polyol (F-9), 2000 parts of methanolwas added. The mixture was subjected to a centrifugal separation at 8000rpm x 60 minutes three times. The separated polymer was washed withmethanol, and dried under reduced pressure at 30 to 40° C., so that 350parts of a polymer was obtained. Further, the polymer was crushed with amortar, and 350 parts of G50 and 1400 parts of methanol were added toform a dispersion. The dispersion was further subjected twice to amechanical dispersing process by a homogenizer (type: 15M-8TA)manufactured by A. P. V. GAURIN, Ltd, which has a homovalve within thedevice and can change the pressure applied to a liquid with a plungerpump. The dispersing process was carried out under the conditions of adispersing pressure of 700 Kgf/cm², a processing rate of 60 kg/hr, and aprocessing temperature of 25° C.

[0409] After the dispersing process, methanol was removed by strippingunder reduced pressure to obtain a polymer polyol (F-10). The polymerpolyol (F-10) produced by the method of the present invention had aviscosity of 5000 mPa·s (25° C.).

Example 10 Production of a Polymer Polyol—10

[0410] The polymer polyol (F-9) obtained in Example 9 was subjectedtwice to a dispersing process by a homogenizer (type: 15M-8TA)manufactured by A. P. V. GAURIN, Ltd., which has a homovalve within thedevice and can change the pressure applied to a liquid with a plungerpump. The dispersing process was carried out under the conditions of adispersing pressure of 700 Kgf/cm², a processing rate of 60 kg/hr, and aprocessing temperature of 25° C. for 2 minutes. After the dispersingprocess, a polymer polyol (F-11) having a viscosity of 9760 mPa·s (25°C.) was obtained.

Comparative Example 1 Comparative Example of the Production of a PolymerPolyol—1

[0411] The comparative polymer polyol (F-9) obtained in Example 9, butnot subjected to the mechanical dispersing process, was used.

Comparative Example 2 Comparative Example of the Production of a PolymerPolyol—2

[0412] Using the same apparatus and method used in the production of(F-9) in Example 9, and using 150 parts of G50, 280 parts of St, 120parts of AN, 8 parts of GMAP, 442 parts of G50 and 1.6 parts of AVN, acomparative polymer polyol (F-12) having a content of polymer particlesof 40%, a hydroxyl value of 33 mgKOH/g and a viscosity of 5540 mPa·s(25° C.) was obtained.

Comparative Example 3 Comparative Example of the Production of a PolymerPolyol—3

[0413] Using the same apparatus and method used in the production of(F-9) in Example 9, and using 175 parts of G50, 210 parts of St, 90parts of AN, 6 parts of GMAP, 519 parts of G50 and 1.2 parts of AVN, acomparative polymer polyol (F-13) having a content of polymer particlesof 30%, a hydroxyl value of 39 mgKOH/g, and a viscosity of 2000 mPa·s(25° C.) was obtained.

Examples (1) to (11) and Comparative Examples 1 to 3 Production ofPolyurethane Foams

[0414] Using the polymer polyols (F-1 to F-8, F-10 and 11) of thepresent invention and the comparative polymer polyols (F-9, F-12 and 13)obtained in Examples 1 to 10 and Comparative Examples 1 to 3,polyurethane foams were produced by the foaming process below, at themixing ratios of polyurethane foams shown in Tables 1 and 2. Theevaluation results for the properties of these foams are shown in Tables1 and 2.

Preparation Example 11 Production of a Reactive Dispersant (D1)—1

[0415] Into a four-neck flask of 500-milliliter volume equipped with athermoregulator, a mixing blade, and a dropping funnel, 28 parts (0.16mole) of TDI and 0.01 part of TBT was added, and cooled at 30° C., andsubsequently 9 parts (0.07 mole) of HEMA were dropped over 2 hours,while the reaction temperature was maintained at 40 to 50° C. Then, thereaction liquid was put into 963 parts (0.14 mole) of a polyol (a-1) ina four-neck flask of 1 liter volume equipped with a thermoregulator, amixing blade, and a dropping funnel, and stirred for 4 hours at areaction temperature of 80 to 90° C. It was confirmed by infraredabsorption spectrum that no unreacted isocyanate group was present, anda reactive dispersant (D1-1) was obtained.

[0416] (D1-1) had a hydroxyl value of 20 and a viscosity of 20000mPa·s/25° C., and a ratio of the number of unsaturated groups to thenumber of nitrogen-containing bonds was 0.22.

Preparation Example 12 Production of a Reactive Dispersant (D1)—2

[0417] A reactive dispersant (D1-2) was obtained in the same manner asthat of Preparation Example 1 except that 8 parts (0.07 mole) of HEA wasused in place of 9 parts of HEMA, and that 964 parts (0.14 mole) of thepolyol (a-1) was used in place of 963 parts of the same.

[0418] (D1-2) had a hydroxyl value of 20 and a viscosity of 19500mPa·s/25° C., and a ratio of the number of unsaturated groups to thenumber of nitrogen-containing bonds was 0.22.

Preparation Example 13 Production of a Reactive Dispersant (D1)—3

[0419] A reactive dispersant (D1-3) was obtained in the same manner asthat of Preparation Example 11 except that 1120 parts (0.16 mole) of thepolyol (a-1) was used in place of 963 parts of the same, and that afour-neck flask of 2-liter volume was used.

[0420] (D1-3) had a hydroxyl value of 19 and a viscosity of 25000mPa·s/25° C., and a ratio of the number of unsaturated groups to thenumber of nitrogen-containing bonds was 0.22.

Example 21 Production of a Polymer Polyol Composition—21

[0421] Into a four-neck flask equipped with a thermoregulator, a vacuummixing blade, a dropping pump, a pressure reducing device, a Dimrothcondenser, and an inlet and an outlet for nitrogen, 10 parts of SAN and440 parts of G50 were added, and after substituting nitrogen for the airin the flask, heated at 130° C. in the nitrogen atmosphere whilestirring (until the polymerization was completed). Then, a materialpreviously prepared by mixing 250 parts of a 2.2-mole propylene oxideadduct of allyl alcohol (Mn=186, SP=10.2), 150 parts of AN, and 100parts of St, and a material previously prepared by mixing 50 parts ofG50 and 1 part of AVN were dropped continuously over 1 hour usingdropping pumps simultaneously, and polymerization was carried out for 2hours at 130° C. Furthermore, unreacted monomers were removed bystripping under reduced pressure. Thus, a polymer polyol composition(F-21) having a content of polymer particles of 50% and a viscosity of4000 mPa·s (25° C.) was obtained.

Example 22 Production of a Polymer Polyol Composition—22

[0422] Into a four-neck flask identical to that used in Example 21, 10parts of SAN and 440 parts of G50 were added, and after substitutingnitrogen for the air in the flask, heated at 130° C. in the nitrogenatmosphere while stirring (until the polymerization was completed).Then, a material previously prepared by mixing 200 parts of a compoundhaving an acetoacetyl group expressed by a formula [6] shown below(Mn=215, SP=11.5), 150 parts of AN, and 150 parts of St, and a materialpreviously prepared by mixing 50 parts of G50 and 1 part of AVN weredropped continuously over 1 hour using dropping pumps simultaneously,and polymerization was carried out for 2 hours at 130° C. Furthermore,unreacted monomers were removed by stripping under reduced pressure.Thus, a polymer polyol composition (F-22) having a content of polymerparticles of 50% and a viscosity of 4000 mPa·s (25° C.) was obtained.

CH₂═C(CH₃)COOCH₂CH₂OCOCH₂COCH₃  [6]

Example 23 Production of a Polymer Polyol Composition—23

[0423] Into a four-neck flask identical to that used in Example 21, 10parts of SAN and 440 parts of G50 were added, and after substitutingnitrogen for the air in the flask, heated at 130° C. in the nitrogenatmosphere while stirring (until the polymerization was completed).Then, a material previously prepared by mixing 50 parts of a compoundhaving a ring-opening lactone chain expressed by a formula [7] shownbelow (Mn=300, SP=10.4), 200 parts of AN, and 250 parts of St, and amaterial previously prepared by mixing 50 parts of G50 and 1 part of AVNwere dropped continuously over 1 hour using dropping pumpssimultaneously, and polymerization was carried out for 2 hours at 130°C. Furthermore, unreacted monomers were removed by stripping underreduced pressure. Thus, a polymer polyol composition (F-23) having acontent of polymer particles of 50% and a viscosity of 4200 mPa·s (25°C.) was obtained.

CH₂═CHCO[O(CH₂)₅CO]₂OH  [7]

Example 24 Production of a Polymer Polyol Composition—24

[0424] Into a four-neck flask identical to that used in Example 21, 10parts of SAN and 440 parts of G50 were added, and after substitutingnitrogen for the air in the flask, heated at 130° C. in the nitrogenatmosphere while stirring (until the polymerization was completed).Then, a material previously prepared by mixing 180 parts of a compoundhaving a succinic acid residue expressed by a formula [8] shown below(Mn=230, SP=11.2), 160 parts of AN, and 160 parts of St, and a materialpreviously prepared by mixing 50 parts of G50 and 1 part of AVN weredropped continuously over 1 hour using dropping pumps simultaneously,and polymerization was carried out for 2 hours at 130° C. Furthermore,unreacted monomers were removed by stripping under reduced pressure.Thus, a polymer polyol composition (F-24) having a content of polymerparticles of 50% and a viscosity of 4900 mPa·s (25° C.) was obtained.

CH₂═C(CH₃)COOCH₂CH₂OCOCH₂CH₂COOH  [8]

Example 25 Production of a Polymer Polyol Composition—25

[0425] Into a four-neck flask identical to that used in Example 21, 10parts of SAN and 440 parts of G50 were added, and after substitutingnitrogen for the air in the flask, heated at 130° C. in the nitrogenatmosphere while stirring (until the polymerization was completed).Then, a material previously prepared by mixing 250 parts of a compoundhaving a phthalic acid residue expressed by a formula [9] shown below(Mn=336, SP=12.0), 150 parts of AN, and 100 parts of St, and a materialpreviously prepared by mixing 50 parts of G50 and 1 part of AVN weredropped continuously over 1 hour using dropping pumps simultaneously,and polymerization was carried out for 2 hours at 130° C. Furthermore,unreacted monomers were removed by stripping under reduced pressure.Thus, a polymer polyol composition (F-25) having a content of polymerparticles of 50% and a viscosity of 5300 mPa·s (25° C.) was obtained.

CH₂═C(CH₃)COOCH₂CH₂OCO(Ph)COOCH₂CH(OH)CH₃  [9]

[0426] where (Ph) represents an orthophenylene group.

Example 26 Production of a Polymer Polyol Composition—26

[0427] A polymer polyol composition (F-26) having a content of polymerparticles of 50% and a viscosity of 3800 mPa·s (25° C.) was obtained inthe same manner as that of Example 21 except that 10 parts of thereactive dispersant (D1-1) was used in place of 10 parts of SAN as adispersant.

Example 27 Production of a Polymer Polyol Composition—27

[0428] A polymer polyol composition (F-27) having a content of polymerparticles of 50% and a viscosity of 3900 mPa·s (25° C.) was obtained inthe same manner as that of Example 21 except that 10 parts of thereactive dispersant (D1-2) was used in place of 10 parts of SAN as adispersant.

Example 28 Production of a Polymer Polyol Composition—28

[0429] Into a four-neck flask identical to that used in Example 21, 10parts of the reactive dispersant (D1-1), 440 parts of G50, and 80 partsof xylene were added, and after substituting nitrogen for the air in theflask, heated at 130° C. in the nitrogen atmosphere while stirring(until the polymerization was completed). Then, a material previouslyprepared by mixing 250 parts of a 2.2-mole propylene oxide adduct ofallyl alcohol (Mn=186, SP=10.2), 150 parts of AN, and 100 parts of St,and a material previously prepared by mixing 50 parts of G50 and 1 partof AVN were dropped continuously over 1 hour using dropping pumpssimultaneously, and polymerization was carried out for 2 hours at 130°C. After adding 20 parts of water to the reaction product, xylene andunreacted monomers were removed from the reaction product by strippingunder reduced pressure of 10 mmHg at 130° C. for 3 hours. Thus, apolymer polyol composition (F-28) having a content of polymer particlesof 50% and a viscosity of 3100 mPa·s (25° C.) was obtained.

Example 29 Production of a Polymer Polyol Composition—29

[0430] A polymer polyol composition (F-29) having a content of polymerparticles of 50% and a viscosity of 4000 mPa·s (25° C.) was obtained inthe same manner as that of Example 21 except that 10 parts of thereactive dispersant (D1-3) was used in place of 10 parts of SAN as adispersant.

Examples 21 to 29 Production of Polyurethane Foams

[0431] Using the polymer polyol compositions (F-21 to F-29) of thepresent invention obtained in Examples 21 to 29, polyurethane foams wereproduced by the foaming process in Table 3. The evaluation results forthe properties of these foams are shown in Table 3.

[0432] [Foaming Process]

[0433] (1) The temperatures of the polymer polyol and the organicpolyisocyanate were adjusted each to 25±2° C.

[0434] (2) A polymer polyol, a foam stabilizer, water and a catalystwere put into a stainless beaker of 1-liter volume in this order, andstirred and mixed at room temperature (25±2° C.). Immediately, anorganic polyisocyanate was added. Using an agitator (Homodisper;manufactured by TOKUSHU KIKA INDUSTRIES, Ltd.; stirring condition, 2000rpm×6 seconds), the mixture was stirred, and foaming was carried out.

[0435] (3) After stopping stirring, the content was put into a woodenbox of 25×25×10 cm, and a polyurethane foam was obtained. TABLE 1Example (1) (2) (3) (4) (5) (6) (7) (8) Polymer Polyol F-1 F-2 F-3 F-4F-5 F-6 F-7 F-8 Concentration of polymer 50 55 45 60 50 50 50 50partides [mass %] Hydroxyl value [mgKOH/g] 28 25 31 22 28 28 28 28Viscosity (25° C.) 4500 4800 4000 6200 4700 4900 5500 5640 [mPa · s]Upper limit of viscosity 7800 13100 4900 23300 7800 7800 7800 7800 inthe inequality (1) (25° C.) [mPa · s] Polyol-soluble polymer 2 1 1 2 2 25 5 [mass %] Dispersionstability ◯ ◯ ◯ ◯ ◯ ◯ ◯ ◯ Polyurethane Foam[mixing ratio (parts)] Polymer polyol 100 100 100 100 100 100 100 100Water 2.7 2.7 2.7 2.7 2.7 2.7 2.7 2.7 Catalyst A 0.18 0.18 0.18 0.180.18 0.18 0.18 0.18 Catalyst B 0.10 0.10 0.10 0.10 0.10 0.10 0.10 0.10Catalyst C 0 0 0 0 0 0 0 0 F-242T 1.0 1.0 1.0 1.0 1.0 1.0 1.0 1.0 TDI-8031.1 30.6 31.6 30.1 31.1 32.0 32.0 32.0 Foam Properties Density [kg/ml]33.5 33.8 33.3 33.8 33.9 33.4 33.6 33.9 25% ILD [kgf/314 cm²] 41.8 42.741.6 44.3 41.4 43.3 41.5 41.0 Tensile strength [kgf/cm²] 1.49 1.40 1.481.35 1.46 1.46 1.48 1.49 Tear strength [kgf/cm] 0.84 0.81 0.85 0.92 0.810.82 0.83 0.78 Elongation [%] 71 69 70 66 68 70 70 68 Resilience [%] 3130 31 27 30 28 26 25 Air Flow [ft³/min] 2.9 3.2 2.8 2.2 3.1 2.8 2.9 3.2Compression set [%] 31.4 33.0 31.3 36.0 33.0 32.5 31.4 33.0

[0436] TABLE 2 Example Comparative Example (9) (10) (11) (1) (2) (3)Polymer Polyol F-10 F-11 F-6 F-9 F-12 F-13 Concentration of polymer 5050 50 50 40 30 particles [mass %] Hydroxyl value [mgKOH/g] 28 28 28 2833 39 Viscosity (25° C.) [mPa · s] 5000 9760 4900 20000 5540 2000 Upperlimit of viscosity in the 7800 7800 7800 7800 3200 1580 inequality (1)(25° C.) [mPa · s] Polyol-soluble polymer 0 6 2 10 8 6 [mass %]Dispersion stability ◯ ◯ ◯ Δ Δ Δ Polyurethane Foam [mixing ratio(parts)] Polymer polyol 100 100 100 100 100 100 Water 2.7 2.7 2.7 2.72.7 2.7 Catalyst A 0.18 0.18 0.18 0.18 0.18 0.18 Catalyst B 0.10 0.10 00.10 0.10 0.10 Catalyst C 0 0 0.30 0 0 0 F-242T 1.0 1.0 1.0 1.0 1.0 1.0TDI-80 32.0 32.0 32.0 32.0 33.0 33.9 Foam Properties Density [kg/m³]33.7 33.8 32.4 33.4 33.2 33.8 25% ILD [kgf/314 cm²] 45.7 41.7 44.5 40.335.7 32.4 Tensile strength [kgf/cm²] 1.52 1.48 1.52 1.46 1.57 1.66 Tearstrength [kgf/cm] 0.89 0.83 0.86 0.75 0.76 0.71 Elongation [%] 70 70 7465 90 105 Resilience [%] 30 30 32 24 27 28 Air Flow [ft³/min] 3.9 2.92.2 1.3 3.0 3.7 Compression set [%] 28.4 31.4 27.5 37.5 28.2 10.5

[0437] TABLE 3 Example 21 22 23 24 25 26 27 28 29 Polymer Polyol F-21F-22 F-23 F-24 F-25 F-26 F-27 F-28 F-29 Concentration of polymerparticles 50 50 50 50 50 50 50 50 50 [mass %] Viscosity (25° C.) [mPa ·s] 4000 4000 4200 4900 5300 3800 3900 3100 4000 Upper limit of viscosityin the inequality (1) (25° C.) 7800 7800 7800 7800 7800 7800 7800 78007800 [mPa · s] Polyol-soluble polymer [mass %] 1 1 2 2 3 1 1 1 1Dispersion stability (1) ◯ ◯ ◯ ◯ ◯ ◯ ◯ ◯ ◯ Dispersion stability (2) ◯ ◯◯ ◯ ◯ ⊚ ⊚ ⊚ ⊚ Polyurethane Foam [mixing ratio (parts)] Polymer polyol100 100 100 100 100 100 100 100 100 Water 2.7 2.7 2.7 2.7 2.7 2.7 2.72.7 2.7 Catalyst A 0.18 0.18 0.18 0.18 0.18 0.18 0.18 0.18 0.18 CatalystB 0.10 0.10 0.10 0.10 0.10 0.10 0.10 0.10 0.10 F-242T 1.0 1.0 1.0 1.01.0 1.0 1.0 1.0 1.0 TDI-80 30.7 31.4 30.9 31.2 31.7 30.7 30.7 30.7 30.7Foam Properties Density [kg/m³] 33.0 33.1 33.3 33.4 33.0 33.2 33.1 33.233.0 25% ILD [kgf/314 cm²] 43.4 43.2 42.7 43.6 43.1 44.5 44.8 45.1 45.1Tensile strength [kgf/cm²] 1.50 1.48 1.49 1.45 1.36 1.50 1.48 1.49 1.53Tear strength [kgf/cm] 0.19 0.83 0.87 0.89 0.85 0.88 0.92 0.91 0.96Elongation [%] 71 70 71 69 70 70 72 70 75 Resilience [%] 30 32 29 28 3129 31 30 31 Air Flow [ft³/min] 3.0 3.1 2.9 3.0 2.7 2.8 2.6 2.9 2.7Compression set [%] 30.9 32.0 32.7 34.8 32.7 30.1 29.5 29.4 25.3

[0438] The foam properties in Tables 1 to 3 are evaluated by the methodsas follows.

[0439] Density (kg/m³): according to JIS K6400-1997 [item 5]

[0440] 25% ILD (kgf/314 Cm²): according to JIS K6382-1995 [item 5.3]

[0441] Tensile Strength (kgf/cm²): according to JIS K6301-1995 [item 3]

[0442] Tear Strength (kgf/cm): according to JIS K6301-1995 [item 9]

[0443] Elongation (%): according to JIS K6301-1995 [item 3]

[0444] Resilience (%): according to JIS K6400-1997 [item 7]

[0445] Air Flow (ft³/min): using Dow type flowmeter [manufactured byAMSCOR, Ltd.] (test piece 5 cm×5 cm×2.5 cm)

[0446] Compression Set (%): according to JIS K6382-1995 [item 5.5]

[0447] Usually, as the properties of polyurethane foams, a density inthe range of 15 to 50 kg/m³ is preferable, and larger values of 25% ILD,tensile strength, tear strength, elongation, resilience and air flow arepreferable. Furthermore, a smaller value of compression set ispreferable.

[0448] As seen from Tables 1 to 3, the polymer polyols (F-1 to F-8,F-10, F-11, and F-21 to F29) of Examples 1 to 10 and 21 to 29 have lowerviscosities than the polymer polyol (F-9) of Comparative Example 1, andhave more excellent properties, particularly in 25% ILD (hardness), airflow and compression set. Moreover, the polyurethane foams produced fromthe polymer polyols (F-1 to F-8, F-10 and 11) have the same or highertensile strength, tear strength, elongation, and resilience as thoseproduced from the polymer polyol (F-9). Furthermore, because the polymerpolyols (F-12, F-13) of Comparative Examples 2 and 3 have lowerconcentrations of polymer particles than the polymer polyols (F-1 toF-8, F-10, F-11, and F-21 to F-29) of Examples 1 to 10 and 21 to 29 andthe comparative polymer polyol (F-9) of Comparative Example 1, they havelow viscosities. However, the properties of the polyurethane foamsproduced from the polymer polyols (F-12, F-13) are significantlyinferior to the properties of the polyurethane foams produced from thepolymer polyols (F-1 to F-8, F-10 and 11), particularly in 25% ILD(hardness). In general, as the concentration of polymer particlesincreases, the tensile strength, elongation, resilience and air flowdecrease, and the compression set increases. However, the polyurethanefoams using the polymer polyols of the present invention [Examples (1),(5) to (10), and (21) to (29)] exhibit the same or greater propertiesthan the polyurethane foam of Comparative Example 1 having the sameconcentration of polymer particles.

INDUSTRIAL APPLICABILITY

[0449] According to the polymer polyols of the present invention and themethods for producing the same, polymer polyols having low viscositiesand exceptionally good dispersion stability can be obtained, even whenthe polymer polyols have a higher concentration of polymer particlesthan conventional polymer polyols. Thus, the operation efficiency can beimproved significantly in the production of polyurethane resins, etc.

[0450] Furthermore, the polyurethane resins produced using the polymerpolyols of the present invention as an essential component of a polyolexhibit much more excellent 25% ILD (hardness) than those produced usingconventional polymer polyols, when they have the same viscosity.Furthermore, the polyurethane resins produced using the polymer polyolsof the present invention have considerably better 25% ILD, air flow andcompression set than those produced using conventional polymer polyols,when the concentrations of polymer particles the polymer polyols are thesame.

[0451] Because of the above-mentioned effects, the polyurethane resinsproduced using the polymer polyols of the present invention areexceptionally suitable as polyurethane foams for the uses such asinterior parts of automobiles, furniture, and the like.

1. A polymer polyol composition (I) comprising a dispersion medium composed of a polyol (A), or (A) and a diluent (C), and polymer particles (B) dispersed in the dispersion medium, wherein the polymer particles (B) are formed by polymerizing an ethylenically unsaturated compound (b) in a polyol or in a polyol and the diluent (C); a content of (B) in (I) is from 35 to 75 mass %, based on the mass of (I); and an amount of soluble polymers (P) dissolved in (A) is not more than 5 mass %, based on the mass of (A).
 2. A polymer polyol composition (I) comprising a dispersion medium composed of a polyol (A), or (A) and a diluent (C), and polymer particles (B) dispersed in the dispersion medium, wherein the polymer particles (B) are formed by polymerizing an ethylenically unsaturated compound (b) in a polyol or in a polyol and the diluent (C); a content of (B) in (I) is from 35 to 75 mass %, based on the mass of (I); and a viscosity V (mPa·s) of (I) measured by a Brookfield viscosimeter at 25° C. is in the range of an inequality V≦(Va−Va×C/10){circumflex over ( )}[e{circumflex over ( )}x],  (1) where x=0.0010354×Bp{circumflex over ( )}1.5, Va is a viscosity (mPa·s) of (A) measured by a Brookfield viscosimeter at 25° C., C is a content of (C) in (I) (mass %), Bp is a content of (B) in (I) (mass %), symbol {circumflex over ( )} indicates a power, and symbol “e” is the base of the natural logarithm.
 3. The polymer polyol composition according to claim 1, wherein the content of (B) in (I) is from 45 to 75 mass %.
 4. The polymer polyol composition according to claim 1, wherein (b) contains at least 5 mass % of an ethylenically unsaturated compound (b1) having a number-average molecular weight of at least 500; and (b) is polymerized in (A) in the presence or absence of at least one selected from a dispersant (D) and a diluent (C).
 5. A polymer polyol composition (II) comprising a polyol (A) and polymer particles (B) dispersed in a dispersion medium composed of a polyol (A), or (A) and a diluent (C), wherein the polymer particles (B) are formed by polymerizing an ethylenically unsaturated compound (b) in a polyol; (b) contains at least 5 mass % of an ethylenically unsaturated compound (b1) having a number-average molecular weight of at least 500; and (b) is polymerized in the presence of a dispersant (D), and in the presence or absence of a diluent (C).
 6. The polymer polyol composition according to claim 4, wherein a molecular weight (X) per one double bond of (b1) is not more than
 1200. 7. The polymer polyol composition according to claim 4, wherein (b1) is an ester of an unsaturated carboxylic acid (p) with a glycol (q), and/or an ester of an unsaturated alcohol (r) with a carboxylic acid (s).
 8. The polymer polyol composition according to claim 7, wherein the unsaturated carboxylic acid (p) is at least one carboxylic acid selected from maleic acid, fumaric acid and itaconic acid.
 9. The polymer polyol composition according to claim 1, wherein the polymer particles (B) are separated from a polymer polyol composition obtained by polymerizing (b) in a polyol, and mechanically dispersed in (A) not containing more than 5 mass % of soluble polymers, based on the mass of (A).
 10. A polymer polyol composition (III) comprising a polyol (A) and polymer particles (B) dispersed in a dispersion medium composed of a polyol (A), or (A) and a diluent (C), wherein the polymer particles (B) are formed by polymerizing an ethylenically unsaturated compound (b) in a dispersion medium comprising (A) in the presence of a dispersant (D′) to form polymer particles, and mechanically dispersing or crushing the polymer particles, and wherein a difference between a solubility parameter SPd of (D′) and a solubility parameter SPa of (A) is not more than 0.8.
 11. A method for producing a polymer polyol composition (I) according to claim 1, which method comprises polymerizing an ethylenically unsaturated compound (b) in a polyol (A) in the presence or absence of at least one selected from a dispersant (D) and a diluent (C), wherein the polymer polyol composition is obtained using (b) containing at least 5 mass % of an ethylenically unsaturated compound (b1) having a number-average molecular weight of at least
 500. 12. A method for producing the polymer polyol composition (I) according to claim 1 comprising a polyol (A) and polymer particles (B) dispersed in (A), which method comprises separating the polymer particles (B) from a polymer polyol composition obtained by polymerizing an ethylenically unsaturated compound (b) in a polyol; and mechanically dispersing the polymer particles (B) in (A) not containing more than 5 mass % of soluble polymers, based on the mass of (A).
 13. A method for producing the polymer polyol composition (III) according to claim 10, which method comprises polymerizing an ethylenically unsaturated compound (b) in a dispersion medium comprising a polyol (A) in the presence of a dispersant (D′) to form polymer particles in a polymer polyol; and mechanically dispersing or crushing the polymer particles, wherein a difference between a solubility parameter SPd of (D′) and a solubility parameter SPa of (A) is not more than 0.8.
 14. A method for producing a foamed or non-foamed polyurethane resin, which method comprises reacting a polyol component with a polyisocyanate component in the presence or absence of a blowing agent, wherein the polymer polyol composition according to claim 1 is used at least as a portion of the polyol component.
 15. The polymer polyol composition according to claim 1, wherein at least 5 mass % of (b) comprises a terminal ethylenically-unsaturated group containing compound (b3) having a number-average molecular weight of 160 to 490 and a solubility parameter SPb of 9.5 to
 13. 16. The polymer polyol composition according to claim 1, wherein the polymer particles (B) are formed by polymerizing the ethylenically unsaturated compound (b) in the dispersion medium composed of the polyol (A), or (A) and the diluent (C), in the presence of 0.5 to 50 mass parts of a reactive dispersant (D1) with respect to 100 mass parts of (A), the reactive dispersant (D1) being an unsaturated polyol having a nitrogen-containing bond, which is formed by bonding a substantially saturated polyol (a) with a monofunctional active hydrogen compound (e) having at least one polymerizable unsaturated group via a polyisocyanate (f).
 17. The polymer polyol composition according to claim 1, wherein the polymer particles (B) are formed by polymerizing the ethylenically unsaturated compound (b) in the dispersion medium composed of the polyol (A), or (A) and the diluent (C), in the presence of 0.1 to 80 mass parts of a reactive dispersant (D11) with respect to 100 mass parts of (A), the reactive dispersant (D11) being an unsaturated polyol having a nitrogen-containing bond, which is formed by bonding a substantially saturated polyol (a) with a monofunctional active hydrogen compound (e) having at least one polymerizable unsaturated group via a polyisocyanate (f), and whose average value of a ratio of a number of unsaturated groups to a number of nitrogen-containing bonds originating from an NCO group in one molecule of (D11) is 0.1 to 0.4.
 18. The polymer polyol composition according to claim 2, wherein not less than 5 mass % of the ethylenically unsaturated compound (b) comprises a terminal-ethylenically-unsaturated-group containing compound (b3) having a number average molecular weight of 160 to 490 and a solubility parameter SPb of 9.5 to
 13. 19. The polymer polyol composition according to claim 2, wherein the polymer particles (B) are formed by polymerizing the ethylenically unsaturated compound (b) in the dispersion medium composed of the polyol (A), or (A) and the diluent (C), in the presence of 0.5 to 50 mass parts of a reactive dispersant (D1) with respect to 100 mass parts of (A), the reactive dispersant (D1) being an unsaturated polyol having a nitrogen-containing bond, which is formed by bonding a substantially saturated polyol (a) with a monofunctional active hydrogen compound (e) having at least one polymerizable unsaturated group via a polyisocyanate (i).
 20. The polymer polyol composition according to claim 2, wherein the polymer particles (B) are formed by polymerizing the ethylenically unsaturated compound (b) in the dispersion medium composed of the polyol (A), or (A) and the diluent (C), in the presence of 0.1 to 80 mass parts of a reactive dispersant (D11) with respect to 100 mass parts of (A), the reactive dispersant (D11) being an unsaturated polyol having a nitrogen-containing bond, which is formed by bonding a substantially saturated polyol (a) with a monofunctional active hydrogen compound (e) having at least one polymerizable unsaturated group via a polyisocyanate (f), and whose average value of a ratio of a number of unsaturated groups to a number of nitrogen-containing bonds originating from an NCO group in one molecule of (D11) is 0.1 to 0.4.
 21. A polymer polyol composition comprising a dispersion medium composed of a polyol (A), or (A) and a diluent (C), and polymer particles (B) dispersed in the dispersion medium, wherein the polymer particles (B) are formed by polymerizing an ethylenically unsaturated compound (b) in the dispersion medium in the presence of a dispersant (D), wherein at least 5 mass % of (b) comprises a terminal ethylenically-unsaturated group containing compound (b3) having a number-average molecular weight of 160 to 490 and a solubility parameter SPb of 9.5 to
 13. 22. A polymer polyol composition comprising a dispersion medium composed of a polyol (A), or (A) and a diluent (C), and polymer particles (B) dispersed in the dispersion medium, wherein the polymer particles (B) are formed by polymerizing an ethylenically unsaturated compound (b) in the dispersion medium in the presence or absence of a dispersant (D), wherein at least 5 mass % of (b) comprises a terminal ethylenically-unsaturated group containing compound (b3) having a number-average molecular weight of 160 to 490 and a solubility parameter SPb of 9.5 to 13, (b3) being at least one compound selected from compounds (b31) to (b35) shown below: (b31): (poly)oxyalkylene (C₂-C₈ in the alkylene group) ether of a terminal unsaturated alcohol (C₃-C₂₄); (b32): compound expressed by a general formula [1] shown below; (b33): compound expressed by a general formula [2] shown below; (b34): compound expressed by a general formula [3] shown below; and (b35): compound expressed by a general formula [4] shown below: CH₂═CRCOO(AO)_(k)COCH₂COCH₃  [1]CH₂═CRCOO(AO)_(k)[CO(CH₂)_(s)O]_(m)(AO)_(n)H  [2]CH₂═CRCO[O(CH₂)_(s)CO]_(m)O(AO)_(n)H  [3]CH₂═CRCOO(AO)_(k)[QO(AO)_(p)]_(r)(O)_(t)H  [4]  where: R represents a hydrogen atom or a methyl group; A represents an alkylene group having 2 to 8 carbon atoms; Q represents a residue obtained by removing two OH groups from a dicarboxylic acid; k represents an integer of not less than 1 that provides a number average molecular weight of not more than 490; n and p represent 0 or integers of not less than 1 that provide a number average molecular weight of not more than 490; s represents an integer of 3 to 7; m and r are integers of not less than 1 that provide a number average molecular weight of not more than 490; and t represents 0 or
 1. 23. A polymer polyol composition comprising a dispersion medium composed of a polyol (A), or (A) and a diluent (C), and polymer particles (B) dispersed in the dispersion medium, wherein the polymer particles (B) are formed by polymerizing the ethylenically unsaturated compound (b) in the dispersion medium, in the presence of 0.5 to 50 mass parts of a reactive dispersant (D1) with respect to 100 mass parts of (A), the reactive dispersant (D1) being an unsaturated polyol having a nitrogen-containing bond, which is formed by bonding a substantially saturated polyol (a) with a monofunctional active hydrogen compound (e) having at least one polymerizable unsaturated group via a polyisocyanate (f).
 24. A polymer polyol composition comprising a dispersion medium composed of a polyol (A), or (A) and a diluent (C), and polymer particles (B) dispersed in the dispersion medium, wherein the polymer particles (B) are formed by polymerizing the ethylenically unsaturated compound (b) in the dispersion medium, in the presence of 0.1 to 80 mass parts of a reactive dispersant (D11) with respect to 100 mass parts of (A), the reactive dispersant (D11) being an unsaturated polyol having a nitrogen-containing bond, which is formed by bonding a substantially saturated polyol (a) with a monofunctional active hydrogen compound (e) having at least one polymerizable unsaturated group via a polyisocyanate (f), and whose average value of a ratio of a number of unsaturated groups to a number of nitrogen-containing bonds originating from an NCO group in one molecule of (D11) is 0.1 to 0.4.
 25. The polymer polyol composition according to claim 1, wherein the polymer particles (B) are formed by polymerizing the ethylenically unsaturated compound (b) in the polyol (A) and the diluent (C), and (C) comprises an aromatic hydrocarbon-based solvent.
 26. A method for producing a foamed or non-foamed polyurethane resin, which method comprises reacting a polyol component with a polyisocyanate component in the presence or absence of a blowing agent, wherein the polymer polyol composition according to claim 21 is used at least as a portion of the polyol component.
 27. A method for producing a foamed or non-foamed polyurethane resin, which method comprises reacting a polyol component with a polyisocyanate component in the presence or absence of a blowing agent, wherein the polymer polyol composition according to claim 23 is used at least as a portion of the polyol component.
 28. A method for producing a foamed or non-foamed polyurethane resin, which method comprises reacting a polyol component with a polyisocyanate component in the presence or absence of a blowing agent, wherein the polymer polyol composition according to claim 24 is used at least as a portion of the polyol component. 